PROGRESS 1N LOW

TEMPERATURE PHYSICS
VII B
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 CONTENTS O F VOLUMES I-VI

VOLUME I

C.J. Gorter, The two fluid model for superconductorsand helium I1 (16 pages)
R.P. Feynman, Application of quantum mechanics to liquid helium (37 pages)
J.R. Pellam, Rayleigh disks in liquid helium I1 (10 pages)
A.C. Hollis-Hallet, Oscillating disks and rotating cylinders in liquid helium I1 (14 pages)
E.F. Hammel, The low temperature properties of helium three (30 pages)
J.J.M. Beenakker and K.W. Taconis, Liquid mixtures of helium three and four (30 pages)
B. Serin, The magnetic threshold curve of superconductors(13 pages)
C.F. Squire, The effect of pressure and of stress on superconductivity (8 pages)
T.E. Faber and A.B. Pippard, Kinetics of the phase transition in superconductors(25 pages)
K. Mendelssohn, Heat conduction in superconductors(18 pages)
J.G. Daunt, The electrodc specific heats in metals (22 pages)
A.H. Cooke, Paramagnetic crystals in use for low temperature research (21 pages)
N.J. Poulis and C.J. Gorter, Antiferromagnetic crystals (28 pages)
D. de Klerk and M.J. Steedand, Adiabatic demagnetization (63 pages)
L. Nkl, Theoretical remarks on ferromagnetism at low temperatures (8 pages)
L. Weil, Experimental research on ferromagnetism at very low temperatures (11 pages)
A. Van Itterbeek, Velocity and attenuation of sound at low temperatures (26 pages)
J. de Boer, Transport properties of gaseous helium at low temperatures (26 pages)

VOLUME I1

J. de Boer, Quantum effects and exchange effects on the thermodynamic properties of liquid
helium (58 pages)
H.C. Kramers, Liquid helium below 1 OK (24 pages)
P. Winkel and D.H.N. Wansink, Transport phenomena of liquid helium I1 in slits and
capillaries (22 pages)
K.R Atkins, Helium films (33 pages)
B.T. Matthias, Superconductivity in the periodic system (13 pages)
 CONTENTS OF VOLUMES I-VI

VOLUME I1 (continued)

E.H. Sondheimer, Electron transport phenomena in metals (36 pages)

V.A. Johnson and K. Lark-Horovitz, Semiconductors at low temperatures (39 pages)
D. Shoenberg, The De Haas-van Alphen effect (40pages)
C.J. Gorter, Paramagnetic relaxation (26 pages)
M.J. Steenland and H.A. Tolhoek, Orientation of atomic nuclei at low temperatures
(46 pages)
C. Domb and J.S. Dugdale, Solid helium (30 pages)
F.H. Spedding, S. kgvold, A.H. Daane and L.D. Jennings, Some physical properties of
the rare earth metals (27 pages)
D. Bijl, The representation of specific heat and thermal expansion data of simple solids
(36 pages)
H. van Dijk and M. Durieux, The temperature scale in the liquid helium region (34pages)

VOLUME 111

W.F. Vinen, Vortex lines in liquid helium I1 (57 pages)

G. Carerj, Helium ions in liquid helium I1 (22 pages)
M.J. Buckingham and W.M. Fairbank, The nature of the A-transition in liquid helium
(33 pages)
E.R. Grilly and E.F. Hammel, Liquid and solid 'He (40 pages)
K.W.Taconis, 'He cryostats (17 pages)
J. Bardeen and J.R. Schrieffer, Recent developments in superconductivity (1 18 pages)
M.Ya. Azbel' and I.M. Lifshitz, Electron resonances in metals (45 pages)
W.J.Huiskamp and H.A. Tolhoek, Orientatien of atomic nuclei at low temperatures I1
(63 pages)
N. Bloembergen, Solid state masers (34 pages)
J.J.M. Beenakker, The equation of state and the transport properties of the hydrogenic
molecules (24pages)
Z. Dokoupil, Some solid-gas equilibria at low temperature (27 pages)
 CONTENTS O F VOLUMES I-VI

VOLUME N

V.P. Peshkov, Critical velocities and vortices in superfluid helium (37 pages)
K.W. Taconis and R. de Bruyn Ouboter, Equilibrium properties of liquid and solid
mixtures of helium three and four (59 pages)
D.H. Douglas Jr. and L.M. Falikov, The superconductingenergy gap (97 pages)
G.J. van den Berg, Anomalies in dilute metallic solutions of transition elements (71 pages)
Kei Yosida, Magnetic structures of heavy rare earth metals (31 pages)
C. Domb and A.R. Miedema, Magnetic transitions (48 pages)
L. Nkl, R. Pauthenet and B. Dreyfus, The rare earth garnets (40pages)
A. Abragam and M. Borghini, Dynamic polarization of nuclear targets (66 pages)
J.G. Collins and G.K. White, Thermal expansion of solids (30 pages)
T.R. Roberts, R.H. Sherman, S.G. Sydoriak and F.G. Brickwedde, The 1962 jHe scale of
temperatures (35 pages)

VOLUME v
P.W. Anderson, The Josephson effect and quantum coherence measurements in super-
conductors and superfluids (43 pages)
R. de Bruyn Ouboter, K.W. Taconis and W.M. van Alphen, Dissipativeand non-dissipative
flow phenomena in superfluid helium (35 pages)
E.L. Andronikashvili and Yu.G. Mamaladze, Rotation of helium I1 (82 pages)
D. Gribier, B. Jacrot, L Madhavrao and B. Farnoux, Study of the superconductive mixed
state by neutron-diffraction (20 pages)
V.F. Gantmakher, Radiofrequency size effects in metals (54 pages)
R.W. Stark and L.M. Falicov, Magnetic breakdown in metals (52 pages)
J.J. Beenakker and H.F.P. Knapp, Thermodynamic properties of fluid mixtures (36 pages)
 CONTENTS OF VOLUMES I-VI

VOLUME VI

J.S. Langer and J.D. Reppy, Intrinsic critical velocities in superhid helium (35 pages)
K.R. Atkins and I. Rudnick, Thud sound (40 pages)
J.C. Wheatley, Experimental properties of pure He3 and dilute solutions of He3 in super-
fluid He4 at very low temperatures. Application to dilution refrigeration (85 pages)
R.I. Boughton, J.L. Olsen and C. Palmy, Pressure effects in superconductors (41 pages)
J.K. H u h , M. Ashkin, D.W. Deis and C.K. Jones, Superconductivity in semiconductors
and semi-metals (38 pages)
R. de Bruyn Ouboter and A.Th.A.M. de Waele, Superconducting point contacts weakly
connecting two superconductors (48 pages)
R.E. Glover, 111, Superconductivity above the transition temperature (42 pages)
R.F. Wielinga, Critical behaviour in magnetic crystals (41 pages)
G.R. Khutsishvili, Diffusion and relaxation of nuclear spins in crystals containing para-
magnetic impurities (30 pages)
M. Durieux, The international practical temperature scale of 1968 (21 pages)
 P R O G R E S S IN LOW
TEMPERATURE PHYSICS

EDITED BY

D.F. B R E W E R
Professor of Experimental Physics,
Director of the Physics Laboratory,
University of Sussex, Brighton

VOLUME VII B

1978

NORTH-HOLLAND PUBLISHING COMPANY

AMSTERDAM NEWYORK OXFORD
 0 North-Holland Publishing Company - 1978

AN rights reserved. No part of this publication may be reproduced, stored in a retrieval

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ISBN: Vol VIIB 0 444 85209 3

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PUBLISIERS :

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 PREFACE

The first six volumes in this series were published over the period 1957 to
1970 at the rate of about one every three years. There has now been a gap
of eight years between volumes VI and VII, presenting certain problems of
choice of material, particularly in deciding the claims of the currently most
interesting research, the topics which have developed most significantly
since 1970, and the balance of the volume as a whole.
I have felt that one of the areas of greatest and growing interest - and
not only in low temperature physics - is the behaviour of finite systems with
limited dimensionality, to which is also attached the properties of surfaces.
Hence the general articles by Kosterlitz and Thouless on two dimensional
physics, and the more specific topics of “moderately small” superconductors
by Fink, Bibby and McLachlan, quasi-one-dimensional superconductors
by Gor’kov, and the surface of liquid helium by Edwards and Saam. The
most exciting development of course, since 1970 has been the discovery of
the new phases of liquid 3He in 1971, now known to be superfluid, and I
have yielded to the temptation to give this what may be regarded as excessive
attention in the three chapters by Wheatley, by Brinkman and Cross, and by
Wolfle. To counteract the tendency towards concentration on superfluids,
the articles by Flouquet and by Griiner and Zawadowski describe progress
in the area of magnetism and nuclear orientation that has commanded
interest for a long time and continues to develop.
It is interesting to compare the present volume with earlier ones in the
series. The first few volumes contained about 30 per cent each of liquid 4He,
superconductivity and magnetism, the remaining 10 per cent being con-
cerned with other topics such as molecular physics, thermometry and
semiconductors. (See the preface to volume VI.) Volume I (1957) contained
18 chapters of average length 23 pages with a shortest paper of 8
pages and a longest of 63. Volume IV (1964) had declined to 10 chapters,
but of average length 51 pages (shortest 30 pages, longest 97). Following
changes were less marked. Later articles became less general, more specific
ix
X PREFACE

and, as noted in the preface to volume V, had relatively less text, about the
same number of figures and tables, and more formulae and references.
The tendency towards longer articles has continued in the present volume,
which has 9 chapters averaging 81 pages within a range of 54 to 103 pages.
The authors’ enthusiasm has necessitated dividing volume VII into two
parts, A and By thereby somewhat impairing the balance within each but
making them more manageable in size.
No doubt the tendency to write more and more about narrower topics
reflects the natural development of any science, regrettable as it may be.
It becomes more difficult, especially for experimentalists, to be thoroughly
au fait with detailed developments in particular areas of, say, both super-
conductivity and liquid 4He - much less superfluid 3He despite its bond
of BCS theory with superconductivity. Nevertheless, ground of common
and fertile interest does exist for low temperature physicists, and for this
reason the “LT” series of conferences (now triennial instead of biennial as
before 1975) continues to be scientifically profitable. It is also the reason for
the publishers’ decision to revive this series of books after a long gap. To
assume responsibility for Progress in Low Temperature Physics from the
distinguished editorship of C. J. Gorter is a somewhat formidable task.
I shall welcome comments on the structure of this volume as well as suggest-
ions for any future volumes that may appear.
I am grateful to Dr. and Mrs. W. S. Truscott for assembling the name
and subject indexes, and to the publishers for their help in various ways.

Sussex 1978 D.F. Brewer

 CONTENTS
VOLUME VIIA

Preface i x

Contents xi

Ch. 1. Further experimental properties of superfluid 3He, J.C. Wheatley 1

1. Experiments on orbitally related dynamic phenomena in superfluid 3He 3
2. Experiments on spin dynamics 34
3. Experiments of thermodynamic significance 75
4. Recent developments 96
References 101

Ch. 2. Spin and orbital dynamics of superfluid 3He, W.F. Brinkman and
M.C.Cross 105
1.Introduction 107
2.Energetics and superllow 110
3.Singularitiesand textures 134
4.Spindynamics 148
5.Orbitaldynamics 163
Appendix 184
References 188

Ch. 3. Soundpropagation and kinetic coeficients in superfluid 'He, P. WGMe

191
1.Introduction 193
2.Normal Fermi liquid 195
3.Sound propagation in superfluid 3He 209
4.Kinetic coefficients of superfluid 3He 256
5.Conclusion 278
References 279

Ch. 4. Thefree surface of liquid helium, D.O. and W.F. S a m 283

1. Introduction 285
Part 1. Experimental survey 286
2. Surface tension measurements 286
3. The surface tension of pure 3He and 4He 287
4. The surface tension of mixtures of 3He and *He 297
5. Capillary waves. Light scattering at the surface 308
xi
xii CONTENTS

6. Surface second sound. 3He surface currents 310

7. Evaporation and condensation 314
8. The scattering of free atoms at the surface 318
Part 11. Theoretical survey 324
9. The 4He ground state 324
10. 4He excited states 330
11. Theory for dilute solutions of 3He in 4He 347
12. Surface tension of 3He and dilute solutions of 4He in 3He 361
Appendix 363
Notes added in proof 362
References 365
Author index xv
Subject index xxix

VOLUME VII B
Preface ix

Contents xi

Ch. 5 . Two-dimensionalphysics, J.M. Kosterlitz and D.J. Thouless 311

1. Introduction 373
2. Examples of two-dimensional systems 378
3. Phase transitions in two dimensions 389
4. Metal-insulator transitions 420
References 429

Ch. 6. First and second order phase transitions of moderately small super-
conductors in a magnetic field, H.J. Fink, D.S. McLachlan and B. Rothberg
Bibby 435
1. Introduction 437
2. Theoretical results 443
3. Experimental techniques 474
4. Second order phase transitions and the Landau critical point 479
5. First order transitions - superheating and supercooling 489
Appendix 511
List of symbols 512
References 51 3

Ch. 7. Properties of the A-15 compounds and one-dimensionality, L.P. Gor’kov

517
1. Short survey of the properties of the A-15 compounds. Some basic theoretical ideas 519
2. The choice of the electronic term for the linear chain. Instability of the spectrum 529
3. Interactions. Connection between structural and superconductive fluctuations in the
linear chain. The role of the ‘three-dimensional effects’ 533
4. Peculiarities of the three-dimensional electron spectrum in the A-15 lattice due to the
interchain tunnelling. Fine structure of the density of states 544
 CONTENT3 xiii

5.Structure properties of the A-15 compounds in the simplest model. Phonon spectrum
552
6. Some results concerning the superconductivity of A-15 compounds 568
7. Discussion 579
8. Summary.Some concluding remarks 584
References 588

Ch. 8. Low temperature properties of Kondo alloys, G. Griiner and

A. Zawadowski 591
1. Introduction 593
2. Basic models 595
3. The Kondo effect 604
4. Properties below the Kondo temperature 615
5. Phenomenological approaches to the general case 638
6. Conclusions 644
References 645

Cfi. 9. Application of low temperature nuclear orientation to metals with

magnetic impurities, J. Flouquet 649

Introduction 651
1. Comments on nuclear orientation 652
2. Magnetism of an impurity: Kondo effect 669
3. The hyperfine field. The origin of magnetism 689
4. Single impurity effects 698
5. Interaction effects 713
6. Other applications 731
7. Conclusion 734
Appendix 737
References 741

Author index xv

Subject index xxix

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 AUTHOR INDEX TO VOLS. W - B *

Abel, W. R., 732, 741 Andres, K., 318, 484, 664, 669, 731, 365,
Abelh, B., 422,429 513, 741, 742
Abragarn, A., 655, 741 Appleyard, E. T. S., 485, 513
Abraham, B. M., 3,4,5,7,9,204,205,211, Archie, C. N., 7, 9, 12, 18, 36, 80, 81, 82,
102, 279 83, 84, 85, 87, 102
Abraham, E., 386,429,432 Arnold, E., 423,429
Abrikosov, A. A., 208, 535, 611, 614, 676, Arp, V., 442, 714, 726,515, 744
112,279,588.645, 741 Ashkin, J., 408,429
Adarns, E. D., 29,30,31,102 Aslamazov, L. G., 386,429
Adarns. G., 384,431 Atkins, K. R., 285,287,288, 291, 293,296,
Adkins, C. J., 385. 424, 425, 429, 432 308, 314, 332, 334, 365, 366, 367, 368
Ahonen, A. I.. 31, 33, 36, 37, 38, 39, 40, Avenel, O., 63, 96, 143, 732, 101, 188, 741
64,65, 68, 69, 71, 12, 73, 74, 84, 85, 86, Axe, J. D., 523,524,553,564,568,588,589
88,89,142,383,101,188,429
Alexander, S., 419,429 Babic, E., 645
Ali, M., 693, 108, 741 Bagguley, D. M.S., 691, 694, 697, 741
Allen, J. F., 287, 288, 296, 365 Baldwin, J. P., 473,480,486, 488,513, 516
Allen, S. J., 385,424,429,433 Balian, R., 159, 188
Alloul, H., 631, 632, 637, 689, 709, 717, Balibar, S., 324, 366
735, 736, 645, 741, 744 Band, W. T., 4, 6, 9, 21, 28, 31, 92, 265,
Alquie, G., 694, 704, 105, 741 267,268,102,280
Als-Nielsen, J., 404. 407, 429 Baratoff, A., 472,473,516
Alvesalo, T. A., 6, 7, 8, 9, 12, 19, 20, 80, Barber, M. N., 411,430
81, 82, 83, 94, 265, 267, 268, 101, 102, Barclay, J. A., 698, 706, 741
279 Bardeen, J., 299,437,442,468,469,366,513
Arnamou, A., 693, 741 Barham, B., 692,728, 744
Arnbegaokar, V., 50, 110, 112, 113, 130, Barham, D. C., 688,736, 742
131, 158, 422, 429, 625, 101, 188, 429, BarisiE, S., 577,588
433,646 Barnes, L. J., 441,513
Ambler, E., 659, 746 Barrett, C . S., 521,522,588
Arnit, D., 328, 392, 365, 429 Bartoff, A., 441, 457, 471, 476, 417, 491,
Anderson, A. C., 732, 741 496,497,498,502,510,516
Anderson, P. W., 14, 16, 20, 36, 39, 64, Barton, G., 78,101
80, 81, 112, 113, 114. 121, 122, 126, 127. Bassett, A., 643, 645
137, 139, 148, 168, 169, 170. 172, 176, Batterman, B. W., 521, 522, 559. 562, 588,
177, 181, 184, 195, 211, 224, 318, 324, 589
399, 423, 521, 561, 595, 613, 615, 619, Baxter, R. J., 419,429
625, 626, 629, 673, 714, 101, 102, 103, Baym, G., 195,208,299,301,357,279,366
188, 189, 279, 365, 429, 588, 645, 647, Beaglehole, D., 673,645
741, 742 Real-Monod. M. T.,383, 732, 429, 744
Andrew, A. F., 285, 298, 310, 343, 347, Bean, C. P., 442,504,513
352, 356, 359, 365, 365 Beasley, M. R., 473,516
*Volume VII is published in two parts: page numbers 1-370 in the index refer to volume
VII A and page numbers 371-746 refer to volume VII B.
xvi AUTHOR INDEX

Bell, A. E., 645 Boldarev, S. T., 287, 296, 297, 299, 300,
Beloerskij, G. N., 693, 745 305,308,309,366,369
Beni, G., 384,432 Bonsall, L., 427, 430
Benoit, A., 665, 666, 668, 681, 687, 693. Borg. R. J., 714, 717. 745
698, 693, 708, 710, 711, 712, 725, 726, Boucal, F.,692,728,730, 741
731,734,736, 741, 745 Bowley, R. M., 34, I01
Berezinskii, V. L.,381, 390, 392, 393. 407, Boyce, J. B., 688,696,709, 741
409,410,429 Boysen, J., 692,727,729,730, 741
Berezniak,N. G., 287,298,367 Bozhkov, A. I., 309,366
Berglund, M. P.,732,741 Bozler, H. M.,10, 210, 102, 280
Berlin, T. H., 390,430 Bozorth, R. M., 693, 741
Berman, H. S., 581,589 Bradley, P.E., 475,513
Bernas, B., 509,513 Brandt, D., 315,366
Bernier, M. E., 63,96,143,101, 188 Brandt, E. H., 474,513
Berthel, K. H., 578, 589 Breed, D. J., 389,430
Berthier, C., 636,646 Brenig, W., 611, 612,646
Berthold, J. E., 92, 93, 94, 382, 101, 430 Bretz, M., 382,413,430
Betbeder-Matibet, O., 182, 211, 188, 279 Brewer, D. F., 286, 382, 383,726, 366,430,
Betts, D. D., 390,430 432, 745
Beun, J. A., 659,743 Brewer, W. D., 669,683,692,693,706,708,
Bhatnager, A. K.,386,430 725, 126, 727, 729, 730, 741, 742, 745
Bhatt, R. N., 588, 589 Brezin, E., 392, 393,402,405, 430
Bhattacharyya, P., 3, 6, 7, 8, 21, 28, 56, Brinkman, W. F., 3, 20, 42, 44, 45, 46, 56,
63, 256, 267, 268, 273, 277, 101, 103, 59, 64,65, 66, 68, 69, 70, 71, 1.12, 113,
279,280 114, 115, 116, 119, 121, 122, 126, 127,
Binder, K.,404,405,428, 430,433 128, 130, 132, 134, 137, 139, 141, 142,
Birgenau, R. J., 388, 404, 407, 523, 564, 143, 148, 150, 151, 153, 155, 156, 157,
429,430,589 168, 184, 195, 211, 101, 102, 188, 189,
Birks, A. R., 207,280 190,279
Birman, J. L.,557,589 Bristow, J. R., 485,513
Bishop, D. J., 382,429,433 Brodale, G. E., 733,742
Black, W.C., 732, 741 Brooker, G. A., 202,209,279
Blaha, S., 21, 139, 101, 188 Brout, R., 714, 744
Blair, D. G., 316,366 Brouwer, W., 293, 334,366
Blandin, A., 597, 601. 669, 670, 691, 698, Brown, T. R., 384,421,431
714,717,646,741,742 Browne, M. E., 714,726, 744
Blank, A. Ya., 392, 393,407, 429 Buchholz, F. I., 315,366,369
Blatt, J. M., 186, 188
Bucholtz, L. J., 134, 146, 188
Blaugher, K. D., 586,589
Bleaney, B., 655, 741 Bucker, E., 520, 552, 557, 558, 589
Blin Stoyle, R. J., 652, 658, 741 Budnick, J. I., I 14, 742
Bloembergen, P.,389,406,430 Burger, I. P. 442, 477, 486, 490, 496, 509,
Bloomfield. P.E., 612, 646 694,704,705,513,514, 741
Blot, J., 438, 477, 480, 486, 489, 491, 509, Burns, M.J., 384,486,431, 516
516 Butler, D. M., 420,430
Blount, E. I., 56, 64,65, 71, 112, 113, 114, Bychkov, Yu. A., 533,534, 543,589
141,143,521,561,101.188.588
Blumberg, R. H., 472,514
Boata, G., 504,692,513, 744 Callinaro, G., 504,513
BObel, G., 504,613 Cameron, J. A,, 662,692, 741
Bogoliubov, N. N., 224,279 Camp, W.J., 403, 430
 AUTHOR INDEX xvii

Campbell, I. A., 662, 673, 691, 692, 694, Cornbescot, R., 20,110,118,154,158,163,
697, 706, 707, 709, 724, 741, 742, 743, 169, 171, 174, 179, 180, 181, 182, 183,
744,745,746 188, 234, 251, 252, 254, 276, 101, 188,
Cannella, V., 714, 742 279
Caplin, A. D., 608, 630, 692, 645, 646, 742 Compton,J. P., 662,692,709,720,721, 741,
Cardona, M., 441,457, 471,476,477,485, 742
486,491,496,497,498,502,510,514,515, Compton. V. B., 693, 741
516 Cooper, J. R.,608,645
Carneiro, K., 378,433 Cooper, L. N., 442,468,469,513,514
Caroli, B., 674,718, 742 Coqblio, B., 681, 691, 698, 711, 742
Caroli, C., 318, 324,441,366,514 Corak, W. S., 483,514
Caroline, D., 287,296,305,366 Cornut, B., 681,711, 742
Carroll, K. G., 475, 514 Corruccini, L. R., 42.43, 51, 54,55,56, 60,
Casimir, H. B. G., 442,515 65, 66, 69, 70, 71, 83, 89, 90, 121, 141,
Caswell, H. L., 476,488,514 150, 153, 163, 207, 101, 103, 189, 279
Caudron, R., 693, 741 Costa Ribeiro,P., 693,726,730,741,742
Chambers, R. G., 469,514 Cox, M. A. A., 422,430
Chm, S.-K., 425,430 Craig, P. P.,693, 742
Chang, C. C. 321, 325, 328, 332, 338, 341, Crangle, J., 693, 707, 742
351, 362,366 Cross, M. C., 3, 14, 16,20, 26,28, 56,110,
Chapellier, M., 693, 724, 725, 731,741,742 114, 117. 118, 120, 134, 139, 169, 170,
Chechetkin, V. R., 269,279 174, 175, 178, 179, 180, 181, 183, 185,
Cheng, D., 205,279 223, 296, 101, 188, 279, 368
Chernikova, D. M., 315,366 Crow, J. E., 386,430,432
Chester, G. V., 321, 327, 328, 368 Crum, D., 287,297,300,301,302,305,312,
Chester, M.,382, 412,430 313,366
Chock, E. P., 698, 699, 700, 735, 745 Cunsolo, S., 308,366
Chouteau, G., 724, 742 Czenvonko,J., 90,101
Christiansen, P. V., 441,502,514
Chui, S. T., 429,433
Cipolla, J. W.,316, 366 Dalmasso, C., 460,504,514
Cladis, P. E., 125, 188 Dalton, N. W., 422,430
Clark, R. C., 307,366 Daniel, E., 656, 670, 742
Clark, W. B., 388,433 Daniels, J. M., 659, 742
Clarke, J. S., 207,279 Darken, L.S., 475,514
Clogston, A. M., 521,526,589 Dash, J. G., 361, 378, 381, 382, 383, 409,
Cochran, J. F.,483,514 412, 413, 414, 419, 420, 366, 430, 431,
Cody, G. D., 477, 485, 486, 496, 521, 523, 432,433
552, 582,514,515,589 Daunt, J. G.,307, 308,367
Cohen, M., 321, 325, 328, 332, 338, 341, Davidov, D., 698,699,700, 735, 745
351, 362,366 Davis, D. D., 693, 741
Cohen, R. W., 521, 523, 552,582,589 Davis, J. H., 475, 514
Daybell, M.D., 692, 742
Cole, M. W., 318, 328, 384, 412, 366, 430
DeBlois, R. W., 442, 504,514
Coles, B. R., 735,743 d&nnes,P. G., 110, 112, 113, 124, 130,
Collan, H. K., 6, 8, 9, 94, 265, 267, 268, 131, 137, 144, 170, 181, 389, 398, 461,
101, 279 464,465,466,467,577,188,189,430,516,
Collier, R. S., 477,480, 514 588
Collings, E. W., 692, 742 De Groot, S. R., 167,652,189, 743
Combescd, M., 180, 181, 234, 251, 252, de Jongh, L.J., 388,404,408,430
254,188,279 De la Cruz, P.,476,485,486,496,514,515
xviii AUTHOR INDEX

Delaplace, R.,668, 698, 711, 712, 741 Edwards. D.O., 287, 288, 289, 291, 292,
Delrieu, J. M., 31, 125, 173, 174, 102, 189 293, 294, 295, 296, 297, 299, 300, 301,
Denestein, A., 308,367 302, 303, 304, 305, 307, 308, 310, 312,
De Rosa,F., 385,429 313, 316. 317, 318, 319, 320, 321, 323,
de Shone, C., 351,368 324, 328, 334, 335, 338, 342, 343, 347,
DeSorbo, W., 442,504,514 350, 360, 361, 366, 367, 368
Deutscher, G., 477,486, 509,513,514 Edwards, J. T., 423,430
Devaraj, N., 287,288,296,366 Edwards, S. F., 714, 742
De Waele, A. Th.A. M.,664, 746 Ehrenfest, P., 482,514
De Wijn, H. W., 388,430 Eilenberger, G., 110.188
Dickson, D. P. E., 287,296,305,366 Einzel, D., 259,267,271,273,277,279,281
Di Crescenzo, E., 476, 485, 486, 487, 489, Elgin, R. L.,413,417,430
514 Elleman, D. D., 316,368
Dieterich, W., 557,558,589 Elliott, C. J., 390, 430
Di Salvo, F. J., 386,425,433 Emerson, D. J., 726, 745
Disatnik, Y.,300,366 Emery, V. J., 205,279
Ditzian, R. V., 390,430 Engelsberg, S., 56, 64, 65, 66, 68, 69, 70,
Dmitrenko, I. M.,502,516 71,116,119, 126,127,128,132, 134.141.
142, 143, 156, 157, 102, 103, 189, 190
Dobbs, E. R., 207,280
Englert, Th.,385,430
Doezma, R. E., 598,646 Ericson, T.,693, 742
Do Kim Chung, 733, 745 Esel’son, B. N., 287,298, 307,367
Doll, R.,475,477,479,491,514 Esfandiari, M. R.. 439, 452, 453, 454, 462,
Domb, C., 422,430 464,465,466,467, 500,514
Doniach, S., 383, 429, 731, 429, 433, 743 Eska, G., 669,742
Donze, P.,735,743 Essam, J. W., 421,422,430,433
Doran, J. C., 710, 742 Everitt, C. W.F., 308, 367
Dorokhov, 0. N., 548, 550, 552, 562, 565,
566, 568, 581, 584, 586, 587, 589 Fa&, T. E., 479,490,508,514
Douglass, Jr., D. H., 472, 477, 480, 481, Falicov, L. M.,426,431
483,488,514 Fatouros, P. P., 287, 292, 299, 300, 301,
Drew, H. D., 598,646 310, 312, 318, 319, 320, 321, 322, 323,
Druiker, A. K.. 509,514 324,342,343,347,350,363,366,367
DUM,A. G., 422,430 Feder, J., 301, 324, 438, 441, 475,476, 477,
Dworin, L., 694, 697, 742 478, 490, 491, 492, 493, 494, 496, 497,
498.499.502,507,508,510,367,514,515,
Dy, K. S.. 263,279
516
Dyatlov, I. T.,542,589 Felsch, W., 742
Dynes, R.C.,318,365 Ferrell, R. A., 386, 430
Dzyaloshinskyi, I. E., 533, 534, 535, 543, Fert, A., 694, 697, 736, 742, 745
544,580,588,589 Fertig, W. A., 712, 743
Fetter, A. L., 75,88,92,124, 126,128, ,129,
Ebisawa, H., 20, 151, 152, 209, 211, 227, 134, 144, 145, 146, 101, 102, 188, 189
233,276,102,190,279,280 Feynman. R. P., 322, 329, 338. 340, 347,
Ebner, C., 294,295,301,321,328,357,366, 381,367,430
367 Fields, J., 731, 743
Echenique, P. M., 319, 320, 342, 366 Fine, H. L., 386,432
Eckardt, J. R.. 287,288,289,292,293,294, Finger, M.,733, 745
295, 296, 299, 300, 310, 316, 317, 318, Fink, H. J., 439, 441, 452, 453, 455, 456,
323, 324, 334, 335, 338, 347, 366, 367 457, 461, 464, 465, 466. 467, 506. 510,
Eckert, D., 578,589 513,514,516
 AUTHOR INDW Xix

Fiory, J. A., 717, 744 Gergely. L., 608,646

Fisher, K. H., 717, 742 Giaever, I., 412,514
Fisher, D. S., 395, 430 Giannetta, R., 92,93,94,97, 99, 101, 102
Fisher, I. Z., 293, 368 Giauque, W. F., 733, 742
Fisher, M. E., 389, 390, 406,409, 411,430, Gibbons, D. F., 484,514
431,432,433 Gibbs, J. W., 363,367
Fisher, R. A., 733, 742 Gijsman, H. M., 664, 746
Fisher, R. M., 475,514 Gilbard, P. N., 643,646
Fishman, F., 146,189 Gilijamse, K., 389,430
Flint, E. B., 29, 30, 31, 102 Ginzburg, V. L., 438, 440, 442, 443, 446,
Flouquet, J., 668, 681, 683, 687, 692, 693, 461, 462, 463, 464, 465, 466, 467, 515
698, 699, 706, 708, 709, 711, 712, 724, Gittleman, J. I., 422,429
725, 726, 727, 729, 731, 734, 736, 741, Gladstone, G., 580, 588. 589
742,745 Glasser. M. L., 318,367
Follstaedt, D. M., 688, 736, 742 Glen, M., 422,433
Fomin, I., 56,65, 66,73,116,132, 134,141, Glover, R. E., 386,431
142, 154, 361, 102, 189, 367 Goldberg, I. B., 519, 521, 526, 527, 528,
Ford, P. J., 608,646 548,549,578, 579,589
Fowler, A. B., 385,424,431 Goldstein, S., 20, 209,102, 280
Fowler, M., 614, 615,646 Gomes, A. A., 673,743
Fox, R.A., 659,698,733,736, 745 Gongadze, A. D., 129,189
Frankel, R. B., 652, 742 Gonzalez Jimenez, F., 663, 689, 699, 700,
Franks, J., 475,513 735, 743
Freeman, A. J., 652, 690, 742, 743 Goodkind,J. M., 95,96, 102, 103
Fremlin, D. H., 422,430 Goodman, B. B., 496,515
Frenkel, J., 291,367 Goodstein, D. L., 413,417,430
Friedel, J., 398, 415, 417, 418, 425, 595, Gor'kov, L. P., 442,444,497,528,533,534,
598, 656, 670, 673, 679, 714, 430, 646, 535, 543, 544, 548, 550, 552, 562, 565,
741, 742, 743 566, 568, 576, 581, 584, 586, 587, 712,
Friedrich, A., 736, 742 515,588,589,741
Friedt, J. M., 693, 741 Gorter, C. J., 442,655,659,515,743
Frossati, G., 664,701, 702, 718.736, 743 Gorzkowski,W., 529,589
Fu, H. H., 301,367 Gossard, A. C., 728, 744
Fujiki, K., 269, 280 Giitze, W., 611,612, 709,646, 743
Fukuyama, H., 427,428,432 Gould, C. M., 32, 63, 64, 85, 86, 96, 97,
Fulde, P., 557, 558, 589 98,126,143,184,102,189
Fung, H. K., 557, 558, 589 Grace, M. A., 652,658,659,662, 741, 742,
743
Gainon, D., 735, 743 Graebner, J. E., 731, 741
Gallop, J. C., 693, 707, 708, 709, 724, 741, Gra!', P., 475,477,479,491,514
743 Graham, R., 154, 170, 173, 174, 253, 256,
Ganguly, A. K., 557, 589 189,279
Garfunkel, M. P., 490,514 Grant, M. F., 662,692,741
Gasparini, F. M., 287, 288, 289, 292, 293, Grassie, A. D. C., 639,646
294, 295, 296, 299, 300, 310, 316, 317, Grassman, P., 484,515
318,323,324,334,335,338,342,347,366, Greaves, N. A., 77,127,102,189
367 Greytak, T. J., 29, 86,87, 102
Gaunt, D. S., 422,431,433 Griffin, A,, 318,367
Gautier, F., 673, 693, 741, 743 Griffiths, D., 735, 743
Gayda, J. P., 422, 432 Grimes, C. C., 384,430
Geilikman, B. T., 269,279 Gross, E. P.,328,329,365,367
XX AUTHOR INDEX

Griiner, G., 595, 597. 602. 604, 609, 616, Hering, S. V., 413,431
625, 629, 636, 639, 640,641, 643, 644, Hertz, J. A., 391,431
710, 645, 646, 647, 743 Hickernell, D. C., 413, 430
Gubbens, P. C. M., 606,646 Hill, R. W.,662,692, 741
Guernsey, R. W., 4, 7, 92, 265, 102, 279 Hippert, F., 735, 736, 741
Guggenheim, H. J., 388,404,407,429,430 Hiraki, T., 724, 743
Guillou, J. C., 392,405,430 Hirschkoff, E.C., 692,710,718, 743
Gully, W. J., 20, 32, 63, 64, 85, 86. 126, Hirst, L. L., 696, 735, 743
148,,184,209, 102, 189, 190, 280 Hiwonen, hl. T., 693, 742
Gumprecht, D., 693, 745 Ho, T. L.,20,26,28,49,109, 114,117,118,
Gunther, L., 381,431 137, 165, 166, 168, 173, 174, 175, 185,
Guo, H. M., 287, 291, 296, 297, 299, 300, 102,189,190
302, 303, 304, 305, 307, 328, 360, 361, Hockney, R. W., 384,427,431
367 Hohenberg, P. C., 289, 328, 376, 386, 409,
Gurgenishuili, G. E., 129, 189 410,367,431
Guttreund, H., 540,589 Holliday, R. J., 662, 692,727, 729, 743, 744
Guyon, E.,477,486,514 Hollis-Hallett, A. C., 287, 288, 296, 366
Gylling, R. G., 732, 741 Holtzberg, F., 715,730, 743
Hook, J. R..4.6,9,21,28,31,92.164,165,
Hagn, E., 669, 742 l73,174,176,265,267,268,102,I89,280
Hake, R. R., 484,515 Hoppes, D. D., 659, 746
Hall, H. E.,4, 6, 9, 21, 26, 28, 31, 92, 109, Hordb, M., 608,646
120, 164, 165, 173, 174, 176, 265, 267, Hornung, E. W., 733, 742
268,102,189,280 Horovitz, B., 540,589
Halliday, W., 318, 368 Houghton, A., 14, 18, I01
Hallock, R. B., 382, 433 Hu, C.-R., 50, 56, 60,139, 151, 152, 166,
Halperin, B. I., 410,422,429,429,430,433 172, 173, 174, 175, 102, 189, I90
Halperin, W. P., 7, 9,12, 18, 36,80, 81, 82, Huber, J. G., 712,743
83, 84, 85, 87, 102 Huberman, B. A., 429,433
Hamann, D. R., 399, 612, 613, 619, 429, Hudson, R. P., 659, 733, 743, 746
645,646 Huff, G. B., 378,420,430,431
Hamilton, W. D., 733, 745 Hufner, S., 693, 709, 745
Hanak, J. J., 521, 522, 559, 562, 581, 589 Hughes, H. P., 388,432
Handstein, A., 578,589 Huiskamp, W. J., 652, 662, 692, 706, 744
Hanson, M.,692,693,710,743 Hulm, J. K., 586,589
Harden, J. L., 442,515 Hunter, G. H., 315, 367
Hartmann, F., 683,743,745 Huntziger, J. J., 662, 733, 743
Hartstein, A., 385,424,431 Huray, P. G., 725, 745
Hasegawa, H., 689,743 Hyman, D. S.. 318, 323, 324, 367, 369
Hauge, E. H., 401,431
Hauser, J. R.,460,515
Haya, J., 267,268,280 Iche, G., 626,646
Hayano, R.S., 725, 744 Ihas, G. G., 287, 292, 299, 300, 301, 312,
Hayward, R. W., 659,746 318. 319, 320, 321. 323, 324, 342, 343,
Hebral, B., 701,703,736,743 350,367
Hedgcock, F. T., 692,742 Imbert, P., 663, 689, 699, 700, 735, 743
Heeger, A. J., 594,646 Imry, Y.,381,409,431
Heine, V., 425, 430 Indovina, P. L., 476,485,486,487,489, 514
Hemmer, P. C., 401,431 Ishii, H., 638,709,646, 743
Henkel, P. P.,382, 431 Ishikawa, M.,20, 168, 186, 102, I89
Herb, J. A., 382,412,430,431 Ittner, 111, W. B., 473, 515
 AUTHOR INDEX xxi

Ivantsov, V. G., 287,307,367 Khalatnikov, I. M., 173, 208, 257,

Izumov, Yu. A,, 519, 579, 589 308, 330, 346,356, 189, 279, 367
Kharadze, G. A., 129,189
Khmelnitzkii, D. E. 716, 744
Jacarino, V., 521,526, 589 Khor, K. E., 423,431
Jacobs, I. S., 714, 745 Khukhareva, I. S., 485,486,515
Jacucci, G., 308,366 Khutsishvili, G. R., 662, 743
J&n?g, F., 167, 189 Kiewiet, C.W.,4, 6, 9, 21, 28, 31, 92, 265,
Jasnow, D., 409 411,430,431 267,268,102,280
Jensen, H. H., 8, 202, 209, 102, 279 Kikuchi, M., 423,431
Jensen, M. A., 580, 588,589 King, J. G., 318,367
Johnson, C. E.,662, 743 King, P.J., 287, 308, 367
Johnson, R. T., 7, 29, 30, 86, 87, 91, 209, Kinsel, T.,506, 515
244, 245, 251, 252, 265, 267, 268, 102, Kip, A. F., 714, 726, 744
103,279,280 Kirkpatrick, S., 421,422,428,431,432,433
Johnston, W. D., 318, 367 Kiser, S. R., 477, 490, 496, 498, 507, 514
Jones, D. P.,441, 502, 503,515 Kitchens, T. A., 693, 743
Jose, J. V., 428,433 Kittel, C., 460,602,670,674,515,744
Joseph, A. S., 442, 504,515 Kjems, J. K., 378, 413, 414, 431, 433
Josephson, B. D., 48,289,102,367 Klein, E., 693,708, 729,730, 733, 741, 744
Joyce, G. S., 390,406,431 Klein, M. W., 714, 744
Jullien, R., 731,743 Kleinberg, R. E., 18,36,47,103
Kleinberg, R. L., 4, 5, 7, 14,20,29, 30, 36,
87,211,245,249,250,251,252,265,267,
Kac, M., 390, 430, 431 268,102,103,279,280
Kadanoff, L. P., 392, 408, 428, 429, 431, Klbman, M., 134,398,399,190,433
433 Klenin, M.A., 386,430
Kaeser, R. S., 733, 743 Koch, V. E., 238,248,249, 281
Kaiser, A. B., 643,646 Kodama, T., 383,429
Kalfas, C. A., 733, 745 Kogut, J., 392, 433
Kalos, M. H., 321,327,328,368 Kohn, W.,328,367
Kalvius, G. M., 663, 743 Kojima, H.,26, 29, 91, 102
Kamerlingh Onnes, H., 285, 287, 368 Kok, J. A., 483,515
Kammerer, 0. F., 386, 432 Kokko, J., 31,33, 65, 101
Kamper, R. A., 477,480,514 Kompaneets, D. A., 310,314, 343, 356, 359,
Kaplan, J. I., 318, 367 365,365,368
Kaplan, T. A., 390,403,432 Kon, L.Z., 570,589
Karlsson, A., 598, 646 Kondo, J., 594, 604, 690,646, 744
Kasuya, T., 602, 646 Konter, J. A,, 724, 744
Katila, T. E., 693, 742, 743 Kossler, W.J., 717, 744
Kawabata, C., 428,433 Kosterlitz, J. M., 381, 386, 395, 397, 398,
Kawamura, K., 267,268,290 399, 400, 401, 402, 407, 409, 415, 417,
Keck, K., 315,366 419,429,431,433
Kedves, F. J., 608, 646
Kouvel, J. S., 714, 744
Keesom, W. H., 285, 287, 483, 368, 515
Keller, W. E., 287, 367 Kramer, L., 440,510,515
Kellers, C. F., 318,368 Krane, K.S., 698, 734, 744
Kelly, M. J., 426, 431 Kreissler, A., 694,704,705, 741
Kessinger, R. D., 456, 514 Krishnamurthy, H.R.,620, 621, 679, 680,
Ketterson, J. B., 3, 4, 5, 7, 9, 99, 100, 204, 646, 744
205,207,211,234,246,102,103,279,280 Kr06,N.,646
xxii AUTHOR INDEX

Krusius, M., 4,9,10,11, 12, 13, 14, 15, 17, Levitt, D. A., 717,744
19,20, 21, 24, 25, 26, 35, 36, 37, 38, 39, Levy,M., 50, 158, 101,188
40, 64,65, 68, 69,71,72, 73, 74, 84, 85, Lhuillier, D., 173,175,190
86, 87, 88, 89, 142, 143, 175, 265, 383, Li, P. L., 692, 744
101,103,188,189,190,280,429 Liang, N.T.,422,431
Kumar,P., 138,139,147.156,157.189,190 Licciardello, D.C.,385,423,424,431
Kuper, C. G., 318, 324,368 Lieb, E.H.,390,402,431
Kurmaev, E. Z.,519, 579, 580,589 Lifshitz, E. M., 351, 357, 414, 368, 431
Kuroda, A., 428,433 Lines, R.A. G., 662, 692, 741, 742
Kuroda, Y.,93,102 Liniger, W.,472,473,515
Kurti, N.,662,743 Lipson, S. G.,305,368
Liu, K.S.,321,327, 328,368
Labro, M., 692,746 Liu, L. L., 406,431
Lagendijk, I., 692,706,744 Liu, M., 172, 173,190
Laheurte, J. P., 287,307, 308,362,368 Livingston, J. P., 442,504,513
Landau, D. P., 404,405,430 Loegel, B., 693, 741
Landau, J., 305,368 London, F., 442,492,515
Landau, L. D., 195, 200, 250, 298. 351. London, H.,442,485,513,515
357,414,438,442,443,280,368,431,515 Loponen, M. T.,6, 8, 9,94,265, 267, 268,
Landauer, J. K.,484,515 101,279
Landauer, R.,422,431 Loram. J. W., 608,639,707, 646, 744
Landwehr, G., 385,430 Lounasmaa, 0.V., 6, 8, 9, 31, 33, 65, 94,
Lang, H.,316,366 265, 267. 268, 732, 101, 279, 743, 744
Langer, J. S.,412,422,625,429,431,646 Lovejoy, D.R.,287,296,368
Langmuir, I., 373,431 Loyalka, S.K.,316,366
Langreth, D., 624,646 Lubbers, J., 662,744
Larkin, A.I., 386, 533, 534, 543, 716, 429, Luders, G.,497,515
589,744 Lutes, 0.S.,475,485,488,692,515,744
Lasjaunias, J. C., 701,736,744 Luther, A., 402,431
Last, B.J., 422,431 Luttingcr, J. M., 172, 188
Lawson, D. T.,10,20,209,210,102,280 Lyden, J. K.,265,279
Lea, M. J., 207,280 Lynton, E. A., 506,515
Leath, P. L., 422,433
Lecoanet, B.,692,728,730,741 Ma, S. K., 392,429
Le Dang Khoi, V., 691,694, 744 MacLaughlin, D.F., 717, 744
Lederer, P., 707, 744 Magerlein, J. H.,287,288, 289,290,368
Lee, D. M.,10, 20, 32, 63, 64,85, 86, 96, Mahajan, S.,387,425,433
97, 98, 99, 126, 143, 148, 184, 207, 209, Mailfert, R.,521,522, 559, 562,589
210,102,189,190,280 Main, P.C.,4.6,9,21,28,31,92,265,267
Leggett, A. J., 3, 9, 14, 16, 19, 20, 26, 34, 268,102,280
35, 40, 56, 59, 60, 61, 62, 63, 65,66, 68, Maita, J. P., 520, 552, 557,558,589
74,75, 76,77, 78, 79, 81, 82, 92,97,115, Maki, K., 14, 18, 20, 32, 50, 56, 60, 126,
120, 121,122, 123, 125, 127, 148, 158, 138, 139, 147, 151, 152, 154, 156, 157,
163, 169, 177, 178, 179, 180, 182, 183, 209, 211, 218, 227, 233, 386, 102, 189,
184, 185, 186, 187, 195, 211, 223, 258, 190,279,280,431
275,276,277,278,732,102,189,190,280, Maley, M. P., 693,744
744 Maloney, M. D., 476, 485, 486, 496, 514,
Leiderer, P.. 305, 306, 309,368 515
Lekner, J., 347,368 Manchester, F. D., 307,368
Lenglart, P., 673,743 Mandelstam, L., 291,368
Levin, K.,79,80, 88,102 Manhes, B., 692,710, 744
 AUTHOR Imex xxiii

Maple, M. B., 712, 743, 744 Mills, D. L.,707, 732, 744

Mapother, D. E., 493, 515 Mineev, V. P., 120, 134, 137, 138, 139, 171,
Maradudin, A. A., 427,430 183, 184, 185,190
Maraviglia, B., 351, 368 Minier, M., 636, 646
Marcus, P. M., 482,516 Minugerode, G. V., 742
Margenau, H., 354,368 Misener, A. D., 287,288,296,485,365,513
Marsh, J. D., 659, 692, 698, 706, 736, 742, Miyashita, S., 428,433
744, 745 Mizuno, K.,603,646
Marshall, W.,714, 744 Monarka, Y.P., 286,368
Martin, P. C., 166, 167,410, 190,431 Moore, M. A., 78, 390,406,101,432
Martinet, A., 477, 486, 514 Morel, P., 113,168, 184, 188
Matheson, C. C., 316,366 Moriya, 673, 707, 728. 744
Matho, K., 701,703,716,736,743,744 Morris, D. E., 481,515
Mattheiss, L. F., 387,528,431,589 Moskalenko, V. A., 570,589
Matthias, E., 662, 744 Mott, N. F., 385, 422, 423, 424, 425, 432
Mattis, D., 624, 647 Mrozinski, P., 287, 292, 318, 319, 320,
Maxwell, E., 475, 515 342,367
Mazur, P., 167,189 Mueller, R. M., 29, 30,31, 102
McCoy, R. J., 4, 7, 92, 265, 102, 279 Muir, W.R., 692, 744
McEvoy, J. P., 441, 502, 503, 515 Muller-Hartmann, E., 612, 712, 646, 647,
McLachian, D. S., 438, 445, 446, 450, 451, 746
464, 465, 466, 467, 474, 475, 476, 477, Murani, A. P., 699,736, 744
478, 479, 480, 481, 482, 484, 485, 488, Murnick, D. E., 717, 744
489, 491, 493, 494, 496, 497, 498, 499, Murphy, G. M., 354,368
500, 501, 504, 505, 506, 510, 514, 515, Muto, Y.,692, 742
516 Mydosh, J. A., 714, 742
McLean, E. O., 382, 409, 413, 430, 432 Myers, H. P., 598,646
McMillan, W.L., 588, 625,589,645 Myerson, R. J., 429,433
McTague, J. P.. 378, 379, 431, 433
McWane, J., 318,367 Nabarro, F. R. N., 398,415,417,418,445,
Megerle, K., 472, 514 446, 450, 451, 464, 465, 466, 467, 474,
Meinhold-Heerlein, L., 315, 368 475,480,481,482,484,485,488,432,515,
Mendelssohn, K., 382,430 516
Mendoza, E., 287,296,305,366 Nagai, K., 267,268,280
Menyhard, N., 543,621, 626,628,589,646 Nagamine, K., 725, 744
Mermin, N. D., 20, 26, 28, 49, 109, 114, Nagaoka, Y.,611,646
117, 118, 137, 139, 165, 168, 176, 185, Nagasawa, H., 639,646
186, 207, 328, 376, 380, 390, 392, 414, Nagi, A. D. S., 93,102
102, 190, 279, 368, 432 Nagle. D. E., 693, 742
Meyer, D. T., 318,368 Narahara, Y.,287,288,296,366
Meyer, H., 318,368 Narath, A., 659, 688, 692, 694, 695, 697,
Meyer, W. J., 688, 736, 742 728, 735,736, 742, 744, 746
Mezei, F., 636, 646 Narayanamurti, V., 318,365
Michael, P., 475, 478, 479, 485, 489, 491, Nave, S., 725, 745
500,501,515 Nayak, V. S., 301,324,367
Miedema, A. R., 388, 389,404,430 N&l, L.,714, 744
Migdal, A. .A, 392,428,614,432,645 Nelson, D. R.,394,395,404,428,429,430,
Mignot, J. M., 701,702,703,736, 743, 744 432,433
Mihara, N., 329,368 Nemnonov, S. A., 580,589
Miljak. M., 608,646 Newrock, R. S., 692, 744
Miller, R. E., 477, 485, 486, 496, 514, 51 Nichols, T.L.,725, 745
xxiv AUTHOR INDEX

Nielsen, M., 378, 379, 431 Paulson. D. N., 4, 5, 7, 9, 10. 11, 12, 13,
Niesen, L., 692, 706, 744 14, 15, 17, 19, 20, 21, 24, 25, 26, 29, 35,
Nishida, N., 725, 744 86, 87, 89, 91, 143, 175, 209, 211, 244,
Novaco, A. D., 378,413,414, 431 245,249,250,251,252,265,102,103,190,
Nozieres, P., 182, 195, 211, 616, 621, 633, 280
677, 735, 188, 279, 646, 744 Peierls, R. E., 373, 375, 376, 380, 386, 428,
432
Pelcovitz, R. A., 394, 404,432
Obsen, C. E., 698,734,744 Pellan. Y., 438,477,480,486,489,491,509,
Odeh, F., 472, 473, 515 516
Okazaki, M., 423,433 Pena, R., 711,712, 745
Olli, E. E., 316, 368 Pendry, J. B., 319, 320, 342,366
Olsen, J. L., 484, 515 Penrose, O., 409,432
Ono, K., 727, 743 Pepper, M., 385,424, 425,429,432
Ono, Y. A., 267,268,280 Perczuk, B., 698,706,734, 741, 745
Onori, S., 476, 485, 486, 487, 489, 514 Perez-Ramires, J. G., 693, 709, 744, 745
Onsager, L., 373, 375, 390,409, 432 Pershan, P. s.,166, 167, 190
Orbach, R., 689,698,699,700,735,744,745 Peshkov, V. P., 287, 296, 305, 308, 309,
Orsay Group on Superconductivity, 441, 366,368
464, 465, 466,467,515 Peter, M.,689, 744
Osborne, D. V., 315,367,368 Pethick, C. J., 3, 6, 7, 8, 14, 17, 21, 28, 56,
63, 171, 195, 204, 208, 256, 263, 267.
Osheroff, D. D., 36, 39, 42, 43, 51, 54, 55,
268, 273, 277, 101, 103, 190, 279, 280
56, 60, 64, 65, 66, 69, 70, 71, 80, 81, 83,
Pettersen, G., 502, 516
89, 90, 121, 127, 128, 130, 141, 142, 143,
148, 150, 153, 156, 157, 163, 296, 101, Philipps, N. E.. 606, 607, 732, 735, 647,
103,188,189,190,368 741, 745
Pickar, K.A., 308,368
Ott, H. R., 484,731,515, 741
Pinch, H. L.,422,429
Ottavi, H., 422, 432
Pineau, J. C., 438, 477, 480, 486, 489, 491,
Owen, J., 714, 726, 744
509,516
Pines, D., 299,366
Pipman, J., 305,368
Paalanen, M. A., 31, 33, 36, 37, 38, 39, 40,
Pippard, A. B., 469,482,484,515
64, 65, 68, 69, 71, 72, 73, 74, 84, 85, 86,
Platzman, P. M.,384, 385, 427, 428, 432,
88,89,142,383,101,188,429
433
Padmore, T.C., 328,412,368,432 Pleiner, H., 154, 256, 189,279
Pagiola, E., 460, 504,514 Poisel, H., 305, 306, 309,368
Palmer, R. G., 139, 176, 188 Pokrovsky, V. L., 407,569,432,589
Papoular, M.,306,368 Pollak, R. A., 388,432
Park, J. G., 441, 502, 503, 515 Pollitt, S., 385, 424, 425, 429, 432
Parks, R. D., 731, 745 Polyakov, A. M.,392. 393, 402, 404, 432
Parodi, 166, 167,190 Pomeranchuk, I., 298,368
Parr, H., 456, 473,476,478,479,491, 492, Poppema, J. O., 659, 743
493, 495, 496, 498, 499, 502, 506, 507, Potts, R. B., 408, 419,432
508,516 Poulsen, R. S., 441, 457, 464, 465, 466,
Parry, G. S., 388,433 467,516
Passell, L., 378, 413, 414, 431, 433 Pound, R. V.,655, 745
Patani, A., 399,432 Pratt, W.P., 692, 732, 742, 745
Pathria, R. K., 293, 334, 366 Presson, A. G., 439,455,457, 506, 510,514
Patton, B. R., 180, 190 Privorotskii, I. A,, 146, I89
 AUTHOR INDEX xxv

Pryce, M. H. L., 655, 741 Roulet, B., 318, 324,366

Puff, R. D., 329,368 Rudermann, M. A., 602, 670,674, 647, 745
Rudnick, I., 382, 409,432
Quimby, S. L., 484,516 Rush, P., E., 475,513

Rainer, D., 110, 112, 113, 117, 124, 130, Saam, W.F., 287, 294, 295, 304, 307, 308,
131, 144,211, 188, 189, 280 321, 328, 333, 335, 340, 341, 349, 350,
Rasmussen, F. B., 7, 9, 12, 18, 36, 80, 81, 360, 362, 363, 366, 368
82, 83, 84, 85, 87, 102 Sacli, 0.A., 726, 745
Ratto, C. F., 504, 513 Saffren, M. M., 316,368
Rayl, M., 521, 523, 552, 582,589 Sager, R. E., 39, 40, 41, 47, 49, 50, 51, 52,
Reckers, A. B., 664, 746 56,57,58,63,68,73,90,91,150,103,190
Regge, T., 328,368 Sager, R. W., 265,277,278,280
Rehwald, W., 521, 523, 552, 582, 589 Saint-James, D., 318, 324, 442, 460, 461,
Reivari, P., 693, 742 464, 465, 466, 467, 490, 500, 501, 504,
Renard, J. C., 504,516 366,514,516
Renton, C. A., 484,514 Saint Paul, M., 726,730, 742
Reppy, J. D., 4, 7, 21, 28, 31, 92, 93, 94, Sakurai, A., 615,647
382,412,429,101,103,429,431,432,433 Samoilov, B. N., 656, 662, 745
Reut, L. S., 293,368 Sanchez, J., 668, 693, 698, 699, 712, 724,
Reuter, 0.E. H., 469,516 725,726,734,736, 741, 742, 745
Ribault, M., 693, 724, 725, 731, 741 Sanctuary, S., 692,706, 746
Rice, T. M., 388,426,432 Sanders, T. M., 287, 288, 289, 290, 368
Richardson, R. C., 7, 9, 12, 18, 20, 31, 32, Sandiford, D. J., 4,6,9,21,28,31,92,265,
33, 36, 63, 64, 65, 80, 81, 82, 83, 84, 85, 267,268,102,280
86, 87, 126, 148, 184, 209, 383, 101, 102, Sanvinski, R. E.,287, 291, 296, 297, 299,
103,189,280,429 300, 301, 302, 303, 304, 305, 307, 312,
Richer, Y. A., 504,516 313,328,360,366,367,368
Ritchie, D. S., 390, 406, 422, 430, 432 Saslow, W. M., 110, 113, 166, 172, 173,
Rivier, N., 627, 644,646, 647 174,175,188,189,190
Rizzuto, C., 504,595,608,630,513,646 Satterthwaite, C. B., 483, 514
Roach, P. D., 3, 4, 5, 7, 9, 204, 205, 211, Scalapino, D., 402,431
102, 279 Schechter, H., 378,432
Roach, P. R., 3,4, 5, 7,9,99,100,204,205, Schick, M., 381,432
207, 211, 234, 246, 102, 103, 279, 280 Schieffer, J. P.,580, 588, 589
Robertson, J. A., 691, 694, 697, 741 Schlindwein, M., 399,432
Robinson, F. N. H., 659, 742 Schlottmann, P., 709, 743
Robinson, G., 477,488,516 Schmid, A., 386,432
Rogani, A., 476,485,486,487,489,514 Schmidt, H., 119, 167, 171, 386, 189, 530
Rohrer, H., 484, 515 Schmidt, J. L., 692, 744
Rolt, J., 383, 432 Schmidt, R. W.,714, 745
Romagnan, J. P., 287, 368 Schoepe, W., 31, 33,65,383, 101,429
Rose, M. E., 655, 745 Scholtz, J. H., 382, 409,432
Rosenbaum, B., 314,366 Schrieffer, J. R., 442, 468, 469, 602, 624.
Rosenblatt, J., 438, 477, 480, 486, 489, 491, 711,513,647,742,745
509,516 Scott, G. K.,388,426,432
Rothberg, B. D., 475, 488, 516 Scott, W.R., 693, 707, 742
Rothberg, Bibby, B., 437, 445, 446, 450, Scruby, C. B., 388,433
451, 464, 465, 466, 467, 474, 475, 480, Scully, M. O., 318, 324, 367
481, 482, 484, 485, 488, 515, 516 Seiden, J., 269,360,280,368
Rothwarf, F., 477, 490, 496, 498, 507, 514 Seki, H.. 314,366
xxvi AUTHOR INDEX

Seligmann, P., 303, 368 Soda, T., 34, 50,269, 103,280

Senoussi, S., 694, 697, 745 Sblyom, J., 543, 613, 589,647
Seraphim, D. P., 482,516 Sondheimer, E. H., 469,516
Serene, J. W., 117, 180, 211, 212, 218, 227, Souletie, J., 639, 641, 710, 714, 730, 647,
190,280 742, 745
Serin, B., 386, 490, 506, 692,432, 514, 515, Spanjaard, D., 659, 698, 736, 745
744 Stakelon, T., 688, 745
Serwlock, R. G., 662, 743 Stanley, H. E., 390,403,406,408,430,431,
Sevast'yonov, B. K., 485,486,516 432
Shablo, A. A., 502, 516 Star, W. M., 630,631, 639,640,647
Shafi, Q., 399, 432 Steenberg, N. R., 734, 745
Shahzamanian, M., 21, 28,269, 102,280 Steenland, M. J., 659, 743
Shaltrel, D., 689, 744 Steinbeck, M., 47, 92, 265, 102, 279
Shan, Y.,422,431 Steiner, P., 693, 709, 744, 745
Shanabarger, M. R., 692,710, 718, 743 Stepanov, E. P., 656, 662, 745
Shante, V., 421, 432 Stephen, M. J., 445, 446, 450, 451, 464,
Shen, S. Y., 287, 288, 289, 292, 294, 295, 465, 466, 467, 474, 475, 480, 481, 482,
296, 299, 300, 310, 316, 317, 318, 319, 484,485,488,516
320, 323, 324, 342, 347, 366,367 Stephens, J. B., 412,430
Shermer, R. I., 692, 732, 745 Stern, F., 426, 432
Shields, S. E., 95, 96, 102, 103 Stewart, G. A., 381,417,420,430,432
Shih, Y. M., 321, 325, 328, 351,368 Steyert, W. A., 692, 693, 698, 732, 734,
Shikin, V. B., 286, 368 742, 743, 744, 745
Shirane, G., 388, 404, 407, 523, 524, 553, Stillwell, E. P., 475, 514
564, 568,429, 430, 588, 589 Stinchcombe, R. B., 422,432
Shirley, D. A., 652, 662, 733, 743, 745 Stone, N. J., 659, (198,736, 745
Shumeiko, V. S . , 269, 280 Strongin, M., 386, 432
Shvets, A. D., 287, 307, 367 Sudakov, V. V., 542, 589
Siddon, R. L.,381,432 Suhl, H., 611, 647
Sierro, J., 735, 743 Suzanne, J., 378,432
Siggia, E. D., 429,433 Suzuki, M., 428, 433
Simons, A., 385,433 Swallow, G. A., 707, 744
Singh, A. D., 296,368 Sykes, J., 202, 209, 279
Skalyo, J., 388, 404, 407, 430 Sykes, M. F.,389,421,422,430,431,433
Sklijarevskii, V. V., 656, 662, 745 Symko, 0. G.. 692, 710, 718, 742, 743
Skocpol, W. J., 386, 432 Szentumay, Z., 646
Skove, M. J., 475,514
Slichter, C. P., 688, 696, 709, 741 Tai, P. C. L., 473,516
Smith, E. N., 92, 93, 94, 97, 99, 382, 101, Takagi. S., 14, 16, 20, 26, 56, 59, 60, 63,
102,431 74, 158, 163, 169, 177, 178, 179,180, 182,
Smith, F. W., 441, 457, 471, 476, 477, 491, 183, 185, 223, 275, 276, 277, 102, 103,
496, 497,498, 502, 510,516 189,190, 280
Smith, H., 3, 6, 7, 8, 14, 17, 21, 28,42, 44. Takano, Y.,31,33,65,383,101,429
45,46, 56, 63, 64,65, 66, 68, 69, 71, 115, Tam, C. P., 299. 300, 301, 312, 318, 319,
116, 121, 128, 132, 134, 141, 142, 143, 320,324, 342, 350,367
150, 153, 154, 155, 156, 157, 202, 209, Toa, L. J., 698,699,100,735,745
256, 267, 268, 273, 277, 441, 502, 101, Taub, H., 378,413,414,431,433
102,103, 188,190, 279, 280, 514 Taurian, O., 692, 693, 708, 719, 723, 724,
Smith, P. V., 423,431 725,726, 741, 742, 745
Smith, R. 0.. 386.432 Taylor, R.D., 662,693, 742, 743, 744
Sobyanin, A: A., 289,368 Teller, E., 408, 429
 AUTHOR INDEX xxvii

Telschow, K. L., 382,433 van den Berg, 0.J., 594,606,646

Ter-Martirosyan, K. A., 542,589 Van Dyke, J. P., 403,430
Testardi, L. R., 519, 521, 523, 525, 526, Van Scriver, S. W., 413,431
527,528,572,575,578,579,582,587,589 Van Urk, A. T., 285, 287,368
Tholence, J. L., 631, 635, 692, 693, 701, Varoquaux, E. J., 63,96,143,101,188
702, 714, 715, 716, 718, 724, 725, 726, Veillet, P., 691, 694, 744
728, 730,732,647, 741, 742, 743, 745 Vetleseter, A., 732, 741
Thomas, L. K., 693, 745 Veuro, M. C., 6, 8, 9, 94, 265, 267, 268,
Thompson, R. S., 386, 472, 473, 430, 432, 101,279
433,516 Vibet, C.,63, 96, 143, 101, 188
Thomson, J. O., 692, 693, 724, 725, 745 Vieland, L. J., 578, 583, 589
Thomson, J. R., 692, 693, 724, 725, 745 Vig, J., 692, 744
Thouless, D. J., 381, 385, 386, 395, 397, Vilches, 0. E., 413,430,431
398,409,415,422,423,424,430,431,433 Villain, J., 403, 433
Thoulouze, D., 664, 701, 702, 718, 726, Violet, C.E.,714, 717, 745
730, 736, 742, 743, 744 Vochten, M., 692, 746
Tilley, D. R., 488, 516 Volovik, G. E., 20, 120,'134, 137, 138, 139,
Ting, C. S., 557, 558,589 171,183.184,185,103,190
Tinker, R., 318, 367 von Roosbrocck, W., 121, 141, 142, 143,
Tinkman, M., 386, 472, 473,481, 432, 515, 156, 157, 190
516 Vuorio, M., 53, 56, 65, 66, 73, 116, 120,
Tissier, B., 693,697,707, 708, ;56,727, 745 132, 133, 134, 141, 142, 732, 102, 103,
Tolhoeck, H. A., 652, 743 189,190. 741, 744
Tomasch, W. J., 442, 504,515 Vynchier, S.,692, 746
T o m , S.,125,188
Toth, R. W., 420, 430
Tough. J. T., 287, 291, 296, 297, 299, 300, Wagner, H., 376, 390,392,368,432
302, 303, 304, 305, 307, 328, 360, 361, Walker, L. R., 388,430
367,368 Wallace, D. J., 405, 433
Toulouse, G., 121, 134, 137, 176, 398, 399, Wallden, L., 598, 646
425,188,190,433 Wallis, R. H., 385,424,432
Tournier, D., 701,702, 718, 743 Walstedt, R. E., 388,659,717,430, 744, 746
Toumier, R., 631, 635, 692, 693, 701, 702, Wang, J. S. -Y.,460,515
707, 708, 710, 711, 712, 714, 715, 718, Wang, S., 422,431
724, 726, 727, 728, 730, 736, 647, 741, Wang, T. G., 316,368
742, 743, 745 Wanner, M., 305,306,309,368
Toxen, A. M.,472,485,486,516 Warner, D. D., 733,745
Triplett, B. B., 606,607, 735,647, 745 Wassermann, E. F., 693,725,726,732. 741,
Tsui, D. C., 385,424,433 745
Tsuneto, T., 50, 154, 157, 102, 190 Watson, B. P.,422,432,433
Twose, W. D., 423,432 Watson, R. E.,690, 743
Typpi, V. K., 693, 742 Waysand, G., 508,509,514,516
Tzoar, N., 385,433 Webb, R. A., 18, 29, 30, 36, 39, 40,41, 47,
49, 50, 51, 52, 56, 57, 58, 63, 68, 73, 87,
Uimin, G. V., 407,432 90, 91, 150, 265, 267, 268, 277, 278, 102,
Uluer, I., 733, 745 103,190, 279,280
Weeks, J. D., 429,433
Valette, C., 496. 498, 507, 508. 509, 513, Weger, M., 519, 521, 525, 526, 527, 528,
514,516 540,548,549,578,579,589
Valls, O., 79, 80, 88, 102 Wegner, F., 309,390, 405, 408, 431, 433
van Dam, J. E., 606,646 Welber, B., 484, 516
xxviii AUTHOR INDEX

Wernick, J. H., 693, 741 Wolfle, P.,3,4, 5, 7, 9, 11, 27, 75, 112, 113,
Werthamer, N. R., 110,159,172,443,188, 114, 180, 182, 183. 185, 209, 212, 217,
190,516 218, 221, 222, 227, 234, 235, 237, 238,
Weyhmann, W., 692,727,729, 743 243, 244, 248, 249, 259, 267, 269, 270,
Whall, T. E., 608, 646 271, 213, 277, 103, 190, 279, 280, 281
Wheatley, J. C., 3, 4, 5, 7, 8, 9, 10, 11. 12, Woo, C. W., 321, 325, 328, 351, 368, 369,
13, 14, 15, 17, 18, 19, 20, 21, 24, 25, 26, 429
29, 30, 32, 34, 35, 36, 39, 40, 41,44. 45, Woo, J. W. F., 386,429
47, 48, 49, 50, 51, 52, 56, 57, 58, 63, 65, Wu, C. S., 659, 746
68, 73, 74, 77, 79, 80, 81, 83, 84, 85, 86, Wu, F. Y., 390,402,431
87, 88, 89, 90, 91, 93, 95, 97, 143, 150, Wyatt, A. F. G., 287, 308,367
175, 195, 204, 209, 211, 244, 245, 249,
250, 251, 252, 265, 267, 268, 277, 278, Yamada, K., 616, 621, 626, 627, 628, 633,
692, 710, 718, 732, 102, 103, 190, 279, 678,735,647, 746
280, 741, 743 Yamazaki, Y., 725, 744
White, G. K., 484,516 Yang, L. C., 382,412,430
White, R. J., 639, 646 Ying, S. C., 379, 433
Wicklund, A. W., 578, 583,589 Yogi, T., 509, 510, 516
Widom, A., 318, 323, 324,367,369 Yoshida, K., 602, 615, 616, 626, 674, 677,
Widom, B., 287,289,367,369 678,735,647, 746
Wiechert, H., 315, 316,366,369 Yoshimori, A., 615, 629, 677, 647, 746
Wigner, E. P., 427,433 Yoshino, S., 423,433
Wilkins, J. W., 8, 202, 207, 209, 620, 621, Yuval, G., 399,613, 619, 626,429,645, 647
679,680,102,279,646, 744
Will, H., 643, 645 Zavaritskii, N. V., 485, 516
Williams, G., 707, 735, 743, 744, 746 Zawadowski, A., 595, 602, 613, 614, 616,
Williams, I. R., 664, 692, 706, 709, 720, 625, 626, 629, 639, 640. 643, 710, 646,
721, 742 647,743
Williams, P. M., 388, 433 Zdrojewski, W., 693, 745
Williamson, J. S., 509,513 Zeger, R., 557,589
Williamson, S. J., 557, 558, 589 Zener, C., 669, 746
Wilson, G. V. H., 692, 706, 709, 720, 721, Zia, R.K. P.,405, 433
742, 744, 746 Ziman, J. M., 422, 433
Wilson, J. A., 386,425,433 Zinn-Justin, J., 392, 393, 402, 405, 430
Wilson, K., 677, 679, 746 Zinov'eva, K. N., 287, 288, 296, 297, 299.
Wilson, K. G., 392, 619, 620, 621, 679, 300,307, 369
680,433,646,647, 744 Zipfel, C. L., 384, 431
Winzer, K., 742 Zittartz, J., 403, 612, 712, 433, 647, 746
Wolff, P. A., 602, 693, 647, 741, 745 Zlatic, V., 644.647
 SUaJECT INDEX TO VOLS. VIIA-B*

Bulk properties of helium 3; soperfluid phases

unless otherwise stated

bending energies 1 12-1 16,118 magnetic susceptibility, anisotropic A

boundary conditions, A phase 74.114.131 phase 18f, 33
boundary energies, B phase 67, 132f -,Bphase 89ff
boojums 139f mass supercurrent, expression for 111,
113f, 116ff, 120
collective modes of order parameter 4f,
7, 11,27, 210,215,-219 221ff, 230, 239,
243,278 N.M.R., linewidths 63f
collision integral 208, 234-238, 26Of, -, longitudinal ringing frequencies 35-41
263f, 272 -, nonlinear effects 4242,149-153
-, normal 3He 197f, 202f, 208 -, relaxation in 52-55, 158-162
critical flow velocities 29ff -, satellite resonances 96ff
normal locking effect 26,169
dipolar healing length 67.70, 141 144
dipoldipole energy 32f, 35, 122f, 127, orbital dynamics 163-171,173-176
148,154 -, collisionless 177-181
orbital motions, field induced 14ff
electric field orientation 31ff -, persistent 2&25,28
orbital viscosities 170f
fountain pressure 95f order parameter notations 75, 108,217ff
free energy 76,81 orientation cnergks 123-130
hydiodynamic equations 173ff, 182R',
256ff phase diagram 84-87, 89

intrinsic angular momentum density 26,

168,184-188 quasiparticle scattering amplitude 197f
ion mobility 33f 235

kinetic equation, collisionless 212-215, relaxation time, attenuation, t. 6f

259 -, Cooper pairs, h T , TCE 277f
-, hydrodynamic 2652 269f. 275 -, kinetic equation, iK, 7, 237f. 241f,
-, normal 3He 196, 199,201,206 276
- , s ~ a l a r 258ff -, quasiparticle, z. (0) 6f, 9, 18, 63, 262
-, orbital, tl lSff, 26f
Landau parameters 5, 7,90 -, viscous, r, 6-9
Landau theory, normal jHe 195f -, normal 3He,quasiparticle, r ~ ( 0 )
kggett equations 60, 148f 203-2O8,238,245,25Oy262,277f

*Volume VII is published in two parts: page numbers 1-370 in the index refer to volume
VII A and page numbers 371-746 refer to volume VII B.
xxix
xxx SUBJECT INDEX

specific heat 77-83 superfluid density, anisotropic 25, 33,

sound, hydrodynamic 253ff 92ff, 114-118
-, macroscopic regime 2 5 M
-, normal 3He 200-207 temperature scales 84f
-, zero, longitudinal 5, 2Wf, 218, 220, textures, NMR observations of 64-74
224-228,239-248 thermal conductivity 271ff
-, zero, longitudinal, anisotropic 9-13, -, normal 3He 208
227-232, 249f topology of textures 134-140
-, zero, longitudinal, attenuation 4,
225ff, 239,244ff vortices, non-singular 137f
spin relaxation, intrinsic 274-279 viscosity, second 269ff
spin supercurrent, expression for 111, -, shear 6R, 94f, 165-168, 279
114, 116ff, 120 -, shear, normal 3He 204, 207
spin wave spectra 154-1 57
strong coupling parameters 76-80 wall pinned mode, relaxation 56-62, 162f

Free surface of liquid helium

accommodation coefficient 314,316f phonons at surface 293f, 332-335, 337f

capillary waves 308f, 345, 358f reflection coefficient for atoms 319-323,
342
evaporation 314ff, 363 ripplons 287f, 290f, 293ff, 308, 324, 326,
-, velocity distribution 316ff 332-335, 337-341, 344ff, 357, 362f
excited states with surface 330-341,
343-347 scattering at surface, atoms 318f, 324,
341ff, 363
films 3He on 4He, thin 29W, 312. -, light 309, 330
347-351, 352-360 -, neutrons 330, 341
-,thick 302f surface normal density 310f, 344, 346,
356f
ground state with surface 325-329, 362f surface scattering of 3He 313f
surface states of jHe 298-301, 347-351
hydrodynamics of surface 343-346, surface second sound 310f, 344f, 358f
356-360 surface tension 286ff, 363ff
-, 'He 295. 361f
interfacial tension, 3He-4He mixtures -, 4 H ~288-296, 3275 330, 338
305f -, 4He with thin jHe film 297-301. 355
-, 4He with thick 3He film 302f
nucleation of phase separation 360f -, mixtures of 4He in 3He 307, 361f

Two-dimensional physics
(See also Surface of helium: Monolayer of 'He: Surface sound)

absence of long range order 373, 376, Anderson localisation 423f

379f. 386, 394f, 409,414,428
adsorbed atomic films 373, 3781 413, change density waves 387f, 425f
419 crystalline order 3798,413-419
 suBJEa INDEX xxxl

dislocations in 2D solids 41-19 phase transitions 388,39&394

planar rotator 39Of, 395400,402,405,
electrons on surface of helium 373, 3831 410,428f
427f
electrons at surface of semiconductor
renormalisation group 392-395,401,
373, 384%423 428
epitaxial monolayers 419f

king model solution 373, 375. 388, 390, spherical model 376, 390
406f, 419 superfluidity of adsorbed *He 382,
408411,429
magnetic layer compounds 374, 3885
403f, 408 topological order 397, 398ff. 415
magnetic systems, anisotropies in 403-408
metallic layer compounds 374, 386f, 425,
metal-insulator transitions 374, 377, variable range hopping 422f
402426 vortices in superfluid *He 410413,429

percolation model 420ff Wigner lattice 427f

Properties of moderately small superconductors
coherence length 437,446,452,459,462, Ginsberg-Landau equations 438,440,
469,470,472,475,490,494,497 445,457,468,472,474,502,510
critical fields, bulk specimens 439-442, Ginsberg-Landau theory 443,450,463,
444,454,456ff, 473 468,470, 502ff, 507
critical field summaries 464-471
critical field, supercooling 439, 447f, Kappa (Ginsberg-Landau parameter)
450f, 459ff, 468-471,481,488,490ff, 438ff,446,450,452456.458f. 461f.
497f, 500,503 471,485,490,492,496,502ff, 506,
-, superheating 438,4475 49-53, 508, 510
468-471,481,488,49OlT, 4971 500, -, supercooling 492499,501, 504,
502ff, 506,509,510 507
-, surface nucleation 441,459ff; 488, -, superheating 492499,507
491,497,501ff, 506
-, thermodynamic 439,44741,462, Landau critical point 437,448-451, 459,
468471,481,485-489,492 462,468,473f, 476,479,481,483f,
cylinder in axial field 445-451,459f, 463, 487f, 490,499, 505
468,485,487,489 non-local superconductors 468472,497
cylinder in transverse field 453f. 461, nucleation centres 490,4941
463,469,489
penetration depth 437ff, 445,450,452&
delayed flux entry 504 456f, 459,46lff, 471ff, 483,486ff, 490,
492,497,505ff
experimental methods 476-479
quantum oscillations 501
fist order transition 437f. 474,480 sample preparation 47Sf
fluxoids 460,503-506 second order transition 437f, 441,447f.
459, 419, 483,485, 489, 499
Gibbs free energy 438f, 443-447, 452, spheres 453,462,471,476,490-496,
4555 462f, 474,48lf, 484 498%507ff
xxxii SUBJECT INDEX

transition times 508f whiskers 450f, 474f, 481f, 485,488f, 499f

Properties of A-15 compounds

A-15 crystal structure 525, 529 linear chains 525, 529, 546f, 555f, 559,
564f, 579f, 5841
Batterman-Barrett transformation 521ff
526,5335 540, 553, 556f, 561f, 578, 'Parquet' equations 537, 543, 519
%Of, 585

change density wave instability 533-537, relation between structural and super-
539,542f conducting transformations 523, 534,
composition and defects, effects of 523, 544, 564,578, 585
561, 582ff
Cooper instability 534-537, 540-543, softening of phonon spectrum 523f,
569, 571 5321 553f, 5645 579,582, 587
strains, effects of 523, 557, 575, 577
electronic band structure 526-531, 533f, superconducting gap 570f. 573,575, 579
544,548
electronic density of states 520f, 526f, temperature dependence of magnetic
546f, 580 susceptibility 519f, 550-553, 556,558f,
-, logarithmic singularity 547-551, 555, 58lf, 587f
585ff tetragonal distortion parameter 553, 555,
electron-electron interactions 534-538, 5S8f, 562ff, 568.575
588 three-dimensional effects 540. 544-547,
electron-phonon interactions 538f, 554, 553, 566,585
569,586, 588 tunnelling between chains 540, 545,548f

Low temperature properties of Kondo alloys

and applications of nuclear orientation
to metals with magnetic impurities
Abrikosov-Suhl resonance 612,628, gamma-rays, angular distribution 652ff,
640f 660f, 737
analysis of NO experiments 686f gamma-ray anisotropy 656,658f, 683,
Anderson Hamiltonian 596, 670-673, 685, 688
678,691,709 gamma-ray detection and counting 664ff
Anderson model 595-598, 602f, 610, giant moment 701, 704f, 707,718, 726,
620,632ff; 642,644,671ff, 680, 713, 733
718
Anderson model at T =O 624-628.639
angular correlation methods 653, 663 heat capacity of dilute alloys 603, 607,
618. 627,634,663
charge perturbations 599, 601, 625, hyperfine coupling 655, 657,662, 680,
6352 642, 670 682,690-693,697f, 700,702,713,
Edwards-Anderson model 714 717,724,727ff
hyperfine field, effective 684, 686, 700,
Fermi liquid theory 622,624,626, 629, 707,72Off, 724.729
677
Friedel sum rule 598,625
-. saturation 689f. 692f. 698,700. 703.
733
 SUBJECT INDEX xxxiii

implantation techniques 667f radioactive decay schemes 6561

renormalisation group 614, 616
Kondo effect 604f, 607, 612f, 630f, 651, resistivity of dilute alloys 593f, 599ff.
656, 675,731, 735 603% 607ff, 612,628,630f, 634,6391
-, logarithmic approximation 611f 675,703
Kondo temperature 593, 609$ 615, resonances in dilute alloys 596, S98f,
619f, 628ff, 634, 676,679,681f, 706- 601,603, 623,634,639-643
712,726f, 730f RKKY coupling 602,638,670,674,713

magnetic-nonmagnetic transition 594, sample cooling for NO 659, 664

603407,609 sample preparation for NO 665-669
magnetic susceptibility of dilute alloys Schrieffer-WoH transformation 603,
593ff, 606,608,618f, 621,627,630, 620f, 624,643f
632, 6345 680 s-d Hamiltonian 601f, 617, 619, 632,
Massbauer experiments 653,663,687, 634f, 644,669
689. 699f, spin glass 670,704, 713-716, 720ff,
724f, 735
spin polarization 602, 637f, 674
N.M.R. experiments 659,663,687f,
694ff, 7271 735, 736
Nozieres’ F e m i liquid theory 616, thermometry by NO 731f
621ff, 627,677f
Wilson’s numerical solution 594,
‘Poor man’s’ derivation 613f 615-618,622f, 645,677,679
This Page Intentionally Left Blank
 CHAPTER 5

TWO-DIMENSIONAL PHYSICS
BY

J.M. KOSTERLITZ and D.J. THOULESS

Department of Mathematical Physics, University of Birmingham, UK

Progress in Low Temperature Physics, Volume VZZB

Mited by D.F. Brewer
8 North-HollandPublishing Company, 1978
Contents

1. Introduction 373
2. Examples of two-dimensional systems 378
2.1. Classicalfluids and solids 378
2.2. Quantum fluids and solids 381
2.3. Two-dimensional electron gas 383
2.4. Superconductivityin two dimensions 386
2.5. Metalliclayer compounds 386
2.6. Magnetic layer compounds 388
2.7. Smecticliquid crystals 389
3. Phase transitions in two dimensions 389
3.1. Introduction 389
3.2. Magnetic systems 391
3.3. The planar rotator case - topological order 395
3.4. Anisotropies in two-dimensional magnets 403
3.5. Superfluids 408
3.6. Crystalline order in two dimensions 413
3.7. Epitaxial monolayers 419
4. Metal-insulator transitions 420
4.1. The percolation model 420
4.2. Anderson localisation 423
4.3. Density waves 425
4.4. The Wigner lattice 427
Note added in proof 428
References 429
Referencesadded in proof 433
 373

1. Introduction

There have been various important results for two-dimensional systems

obtained over the years, such as Langmuir’s theory of gas adsorption on
surfaces (Langmuir 1918)’ Peierls’ argument for the absence of long-range
order in two-dimensional solids and isotropic ferromagnets (Peierls 1934,
1935), and Onsager’s solution of the two-dimensional Ising model (Onsager
1944). It is only in recent years that a wide variety of two-dimensional systems
have become available for detailed experimental study so that the relevance
of various theoretical ideas could be assessed. At the same time there has
grown up a great interest in the intluence of dimensionality on the behaviour
of physical systems, particularly, but not exclusively, in relation to critical
phenomena near phase transitions.
Various examples of systems which can more or less be regarded as two-
dimensional will be considered in this review. Monolayers of gas adsorbed
onto some substrate provide obvious examples. It is important that the sub-
strate should have a surface which is clean and homogeneous, and helpful if
it has a large surface to volume ratio. Various sorts of finely divided powders,
‘vycor’, which is a porous glass, and ‘grafoil’, which is graphite expanded so
that there are only a hundred or so atomic layers between each surface are all
suitable substrates. Monolayers of inert gases such as helium, neon and argon
can display solid, liquid and gas phases, with properties somewhat different
from the bulk materials. With helium, if the coverage is greater than a single
monolayer, superfluidity can occur at low temperatures, and films of 3He
show the effect of Fermi statistics and the nuclear moments give rise to
important magneticeffects.
There are at least two ways of studying the two-dimensional electron gas.
Firstly it is possible to trap electrons above the surface of liquid helium. The
electrons cannot penetrate the helium because the conduction band is very
high in energy and they cannot leave the surface region because the small
polarizability of helium is sufficientto produce an image charge which attracts
the electrons. It is also possible to produce an ‘inversion layer’ at the surface
of a semiconductor such as silicon by coating the surface with an insulating
oxide layer and then applying a gate voltage on a metal electrode beyond the
314 J.M. KOSTERLITZ AND D.J. THOULESS [CH. 5,g 1

insulating layer which has the effect of bending down the conduction band of
the ptype semiconductor until close to the surface the band lies below the
Fermi level. The same may be done to the valence band of an n-type semi-
conductor. The electrons either on the surface of liquid helium or on the
surface of the semiconductor move freely parallel to the surface if the surface
is sufficiently homogeneous and are bound in a potential well perpendicular
to the surface. In many cases only one level in this potential well is occupied
so the perpendicular degree of freedom is removed and the electrons behave as
a two-dimensionalelectron gas.
Electrons in metallic thin films do not usually behave two-dimensionally,
since the films are generally much thicker than either the wavelength or the
mean free path of the electrons. When such films become superconducting,
however, they may behave two-dimensionally, since the coherence length of
the superconductivitymay be greater than the film thickness. These films are
often somewhat unsatisfactory to study since there may be uncertainty both
in their physical conformation and in their chemical composition. It is also
possible to study superconductivityin the surface of a bulk material in various
ways. For example there is a range of magnetic fields for a type I1 super-
conductor, between H,,and H c 3 ,for which superconductivity occurs in the
surface but not in the bulk.
In the systems mentioned so far there is either a two-dimensional system
attached to the surface of a bulk substrate or the surface of the bulk material
itself forms a two-dimensional system. There are however various materials
which are bulk materials consisting of layers of materials which behave more
or less two-dimensionally. Typical layer compounds are niobium, and
tantalum disulphide or diselenide, which behave electrically as two-
dimensional metals, with a high conductivity parallel to the planes of metal
atoms, and a low conductivity in a perpendicular direction which can be
further reduced by intercalating certain organic materials between the layers.
These particular compounds show a number of interesting phase transitions,
such as the onset of superconductivity and the occurrence of charge density
waves which in some cases lead to a transition between a metallic and a semi-
conducting or semimetallic state. For such layer compounds there is always
some coupling between the layers, and this is likely to dominate close to a
phase transition, since the strong coherence within the layers enhances the
coupling between the layers.
There are also many magnetic layer compounds such as Rb,MnF, in which
there is strong coupling within layers of magnetic atoms and only weak
coupling between the layers, and the difference in these coupling strengths
a.
5.9 11 TWO-DIMENSIONAL PHYSICS 375

may be sufficient for two-dimensional behaviour to be apparent everywhere

except in the immediateneighbourhood of the phase transition.
The smectic phasesof liquid crystalsarealso to someextenttwo-dimensional,
in that they consist of regularly arranged planes of molecules. Phase transitions
occur between the various types of smectic phases, such as the smectioA
phase with the molecular axis perpendicular to the planes and the smectic-C
phase with a tilted axis. There is also in some cases a transition from A, with
a liquid type of disorder in the plane, to the B phase with a solid type of
order.
Probably the main reason for the interest in two-dimensional systems is
that, while they are broadly similar in many respects to three-dimensional
systems, the theoretical analysis is somewhatsimpler. The geometry of a plane
is simpler and more familiar than the geometry of a volume, integrals are
easier to evaluate, and fewer particles need to be studied in a molecular
dynamics or similar numerical computation. All this would be more true of
one-dimensional systems, but they are known to have peculiar properties not
shared by three-dimensional systems. There are particular theories that can be
solved in two dimensions but not in higher dimensions, and problems of
classical statistical mechanics in two dimensions can be related to quantum
ground state problems for one-dimensional many body systems. Apart from
these theoretical points, the study of these two-dimensional systems on
surfaces may provide valuable information about the nature of a surface that
is not readily available from microscopic measurements. For example the
isotherms for gas adsorption give informationabout the area and homogeneity
of the substrate surface.
A major part of the theoretical interest in two-dimensionalsystems has been
concerned with the possibility of phase transitions and the nature of the long-
range order that may occur in these systems, and this subject is covered in
detail in 0 3 of this review. It has been known for forty years (Onsager 1944;
Peierls 1936) that the Ising model has a phase transition in two dimensions,
and it is generally believed that in analogous cases, where the order is des-
cribed by a single real scalar quantity, there will in most cases be it phase
transition from an ordered state at low temperatures to a disordered state at
high temperatures. In many systems, however, the order is described by a
quantity with more than one equivalent degree of freedom, and we use n to
denote the number of degrees of freedom. For example in superfluids and
superconductorsthe ordered state is described by a complex number, so n is 2,
while for the isotropic Heisenberg model of a ferromagnet or antiferromagnet
the order is described by a vector with n = 3. Less obviously n is 2 for the
376 J.M. KOSTERLITZ AND D.J. THOULESS [CH. 5 , s 1

two-dimensional solid since there are 2 degrees of freedom determining the

absolute position of the lattice in space. Peierls (1934, 1935) argued, and
later Mermin and Wagner (1966) and Hohenberg (1967) showed that for such
systems there is no long-range order of the usual type except at zero tempera-
ture, essentially because the thermal motion destroys the order at an arbitrarily
low temperature. The interpretation of this formal result is not so clear. It
may be that at low temperatures the system is almost ordered, with, for ex-
ample, a Debye TZspecific heat at low temperatures in the case of the solid,
but that there is a continuous transition to the high temperature state with no
abrupt change of phase. Measurements of conductivity in superconducting
thin films suggest that for such systems at least this is what occurs. Evidence of
various sorts, from experimental studies, from computer simulations, from
high temperature power series expansions, and from low temperature ex-
pansions has accumulated to suggest that in other cases there may be a sharp
transition despite the absence of long-range order of the type that occurs in
three-dimensionalsystems.
When the number of degrees of freedom n is 2 or more, the two-dimensional
systems are of particular interest in that they are just on the edge of having
sharp phase transitions, so we can speak of 2 as being the ‘lower critical
dimensionality’ of such systems. This is particularly clear in the case of the
spherical model, which is known to be like a magnetic system in which n tends
to infinity, since the failure of the system to order is due to the logarithmic
divergence of an integral for 2 dimensions, and this integral would converge
for 2 + e dimensions however small E is. Although 2 is the lower critical
dimensionality, further study is needed to determine whether or not there is
a phase transition for 2 dimensions, when n is finite. In order to resolve this
problem attention has been focussed on the behaviour of defects in the
ordered phase, and the question of whether they will occur spontaneouslyat
low temperatures. It has been argued on these grounds that the superfluid
and the solid should have a sharp transition, but that the Heisenberg magnet
and other systems with n greater than 2 should not. The problem of defects
such as dislocations in solids and vortices in superfluids leads to an analogy
with a two-component plasma in two dimensions, which somewhat surpri-
singly seems to have an abrupt transition between a neutral and an ionized
state.
In 9 4 we consider a differentclass of problems related to transitions between
metallic and insulating states. The simplest model that displays this behaviour
is the percolation problem, in which a medium is supposed to be made up
randomly of conducting and insulating parts. If the concentration of con-
CH. 5,s 11 TWO-DIMENSIONAL PHYSICS 377

ducting parts is high enough there will be continuous conducting paths across
the system and the medium will conduct, while below a critical concentration
there are no continuous conducting paths and the system is insulating. There
has been considerable study of this problem in two dimensions. It is too
simple a model to be directly relevant to metal-insulator transitions, but it is
actually more relevant to the problem of magnetic alloys, where the magnetic
atoms take the place of the conducting regions and nonmagnetic atoms of
insulating regions; only if there are indefinitely large clusters of magnetic
atoms can the alloy be magnetic.
In the real systems that have been mentioned there are several possible
mechanisms for metal-insulator transitions. In the case of electrons trapped on
a liquid surface it is known that the state of lowest energy is the Wigner
lattice, in which the electrons are confined near to sites on a triangular lattice.
It is not obvious that as the temperature is lowered there will be a sharp
transition to this state, but there is evidence from molecular dynamics calcu-
lations that the transition is sharp. In the inversion layer electron densities are
higher and so the exclusion principle is important. Also the substrate intro-
duces disorder in the potential in which the electron moves, and this results in
localization of the lowest energy electrons even without the influence of
electron-electron interactions. An important feature of localization produced
by disorder in this way is that it is predicted that the conductivity of the
mobile electrons cannot fall below a definite ‘minimum metallic conductivity’.
In two dimensions this minimum metallic conductivity should be a universal
quantity. There is some evidence both from experiment and from numerical
calculations to support this idea.
In the metallic layer compounds the low mobility of the electrons perpen-
dicular to the layers results in a band structure that is almost independent
of the z-component of momentum, so that it is essentially two-dimensional.
The Fermi surface has regions that are almost flat, and this makes it
energeticallyfavourable for a charge density wave to form, which can result
in the production of a band gap resulting from the superlattice formation so
that the system becomes semiconductinginstead of metallic.
This review is not restricted to systems that are studied at low temperatures,
although a number of the phenomena can only be studied at low temperatures.
It is however restricted to problems that are of current interest in fundamental
physics, and it may well be that the most important two-dimensional systems
are excluded as a result. For example there are a number of important
biological processes, such as photosynthesis, that occur on more or less
regular surfaces, and these are not considered here.
378 J.M. KOSTERLITZ AND D.J. THOULESS [CH.5 , # 2

2. Examples of two-dimensional systems

2.1. CLASSICAL
FLUIDSAND SOLIDS

One of the most important examples of two-dimensional systems are pro-

vided by very thin films of volatile atoms or molecules on the surface of a
solid. There has been a recent survey of this topic in the book by Dash (1975),
so here we just mention some of the main features of such systems and the
theoretical problems which arise when they are regarded as two-dimensional
systems.
The usual way of forming and studying a thin film is to have a solid sub-
strate with a large surface to volume ratio while the material to be studied
exists primarily as a gas in the neighbourhood of the substrate and condenses
onto the substrate because of the lower potential energy of the surface, It is
obviously necessary for the substrate to bind the gas molecules more tightly
than they are bound in the bulk liquid for a thin layer to form. The tempera-
ture and chemical potential of the molecules can be controlled by con-
trolling the temperature and pressure of the gas. The number of condensed
molecules can be deduced from the decrease in the volume of the gas from
its bulk value as a result of the presence of the substrate. The area occupied by
the surface layer is the area of the substrate, and this may be measured, at
least in relative terms, if the properties of a standard surface layer are known.
The heat capacity of the surface layer can be deduced from the heat capacity
of the combined system of substrate and gas by subtracting the contributions
of the bulk substances. If the amount of surface material in a small volume is
sufficiently great it is also possible to make structural studies by neutron
scattering or by using the Massbauer effect.
Recent measurements of the heat capacity of Ne monolayers have been
made by Huff and Dash (1976). Argon has been studied using neutron
scattering by Taub et a1.(1975). Kjems et al. (1976)haveused neutron scattering
for monolayers of N, and McTague and Nielsen (1976) for 0,. Schechter
et al. (1976) have used the Miissbauereffect to study butadiene iron tricarbonyl
on grafoil. Earlier measurementsare summarizedby Dash (1975).
These measurements have shown that even the simpler materials such as
the inert gases have a variety of phases, corresponding to gaseous, liquid and
solid phases in the bulk. Various types of solid phase have been observed,some
of which appear to have lattice constants commensurate with the substrate
lattice, while others seem to be incommensurate. For example argon seems
to form an incommensurate triangular lattice on graphite (Taub et al. 1975),
CH.5,821 TWO-DIMENSIONAL PHYSICS 379

and oxygen forms a triangular lattice which is distorted from the close-
packed form below 10 K and is close packed above 10 K (McTague and
Nielsen 1976).
A number of interesting theoretical questions are raised by these results,
but not yet answered by them. Does the existence of something like a gas-
liquid critical point indicate that the phases behave like two-dimensional
gases and liquids? Is there a sharp distinction between phases commensurate
and incommensurate with the substrate, and how are incommensurate phases
modified by the substrate? Does Peierls’ argument for the non-existence of
long-range order in two dimensions mean that the substrate plays an essential
role in the formation of a crystal lattice ofadsorbed gases?
A partial answer to the first question is that the phase diagram of a classical
gas-liquid system tells us rather little about the dynamics of the molecules,
since in classical statistical mechanics the kinetic energy and potential energy
make independent contributions to the free energy. For this reason the
thermodynamic properties of the lattice gas, which would be a realistic model
if molecules were bound to particular lattice sites of the substrate, and of a
model in which the molecules move freely on the surface, are quite similar to
one another. This fact has of course been exploited in the comparison of the
critical behaviour of fluids with the critical properties of the Ising model. To
settle this question it would be necessary to make studies of the diffusion of
molecules on the surface, which will be more or less independent of concen-
tration if the molecules are tightly bound to substrate sites and will be more
rapid in dilute systems (as in a real gas) if the molecules are free to move.
Similarly a strong substrate interaction would be shown up in flow experi-
ments by a frictional force between a flowing monolayer and the substrate.
A detailed study of a model of a two-dimensional lattice interacting with
a regular substrate has been made by Ying (1971). In this work it was found
that the lattice may either adopt the periodicity of the substrate or form a
lattice incommensurate with the substrate. Figure 1 shows possible arrange-
ments of molecules in a periodic potential well due to a substrate. In fig. l a
the molecules are shown at the minima of the potential, with a few molecules
in interstitial positions; this is a first approximation to an arrangement of the
molecules in registry with the substrate. Figure lc shows the molecules as
having relaxed away from the minima in the neighbourhood of the inter-
stitial without losing their long-range registry with the lattice. In such a case
the modes of oscillation will be governed by the potential well, there will be a
minimum of the frequency spectrum, and the lattice specific heat will be of
the Einstein form, exponential at low temperatures. In fig. l b the molecules
380 J.M.KOSTERLITZ AND D.J. THOULESS [CH. 5, $ 2

are shown forming their own periodic lattice incommensurate with the sub-
strate. In fig. Id it is shown how this arrangement may adjust under the
influence of the substrate without losing its own incommensurate period. In
this case there are equivalent arrangements with the same energy obtained
by moving all the molecules shown in fig. l b by a small amount, and then
allowing them to relax again. Because such configurations have the same
energy the phonons have an energy proportional to wave number at low
frequencies, despite the effect of the substrate, and so the specific heat is
Debye-like, proportional to T 2 at low temperatures. Although there are
structure measurements which seem to show incommensurate crystal lattice
for adsorbed molecules, there do not seem to be clean cases of T 2 specific
heats at very low temperatures for classical systems.

(01 Ibl

[Cl Idl

Fig. 1. Possible configurationsfor atoms in a one-dimensional periodic substrate potential.

In case (a) the atoms are in at the potential minima, except for one interstitial atom. In
case (b) the atoms are shown at incommensurate lattice positions. In (c) the atoms have
moved under the influence of interatomic forces away from the positions shown in (a),
while in (d) the atom have moved under the influence of the substrate potential away from
the positions shown in (b).

Peierls’ argument (1934, 1935) for the nonexistence of long-range order in

two-dimensional solids depends on the effect of long-wave phonons, and the
argument of Mermin (1968) depends on a related property of the Hamiltonian.
If phonons of wave number q have an energy ACq then their thermal motion
gives rise to a mean square displacement of the molecules proportional to
k,T/C2q2,and if this is valid for values of q right down to a magnitude of the
order of one over the linear dimensions of the system, the sum over q gives
a mean square displacement which increases logarithmically with the area of
the system. This argument would seem to remain valid in the presence of a
substrate if the lattice is noncommensurateand the specificheat is proportional
to T 2 at low temperatures. If the molecules are in registry with the substrate
there are no low energy phonons and so the argument does not apply.
CH.5,421 TWO-DIMENSIONAL PHYSICS 381

Recently it has been argued that other properties characteristic of the

solid state may exist, even if the type of long range order which gives rise to a
sharp Bragg peak in X-ray scattering is forbidden in two dimensions
(Berezinskii 1970; Kosterlitz and Thouless 1972; Feynman 1973; Imry and
Gunther 1971). It is argued that the long range fluctuations that give rise to
the smearing of the Bragg peak may still leave the structure of the solid distinct
from the fluid, so that there is a quadratic specificheat at low temperatures,and
so that the concentration of dislocations is characteristic of the solid; the
film is rigid rather than fluid. These ideas are discussed in more detail in 6 3.

2.2. QUANTUM
FLUIDSAND SOLIDS

When atoms of helium or molecules of hydrogen or deuterium are adsorbed

onto a surface their small mass is likely to lead to a large zero-point motion,
so that films of helium or hydrogen behave rather differently from films of
heavier molecules. It may be less easy for the molecules to be attached to
particular sites on the substrate so that they may be regarded, to a 6rst approxi-
mation, as moving freely on the surface. Also in the case of helium, which
in the bulk phase remains liquid down to zero temperature,various phenomena
characteristic of quantum fluids can be seen. These systems are also described
in detail by Dash (1975).
At temperatures above 2 K monolayer helium films have a specific heat
of k per atom characteristic of a two-dimensional perfect gas. At lower
temperatures the specific heat of 4He rises to a peak, and there appears to be
condensation to a liquid phase with a critical temperature of 1.4 K. The
specific heat of 'He however drops and there is no sign of condensation.
These results have been explained in detail by Siddon and Schick (1974)
using the quantum virial expansion.
At higher coverages, still in the monolayer region, solid phases of helium
can be formed. These appear to be really incommensurate with the substrate
since the specific heat is quadratic in temperature down to quite low temper-
atures. When the temperature is raised the specific heat rises to a peak and
then drops again to its value in the fluid phase. It is not however clear whether
this specific heat peak represents a sharp phase transition, but there is a good
deal of indirect evidence that it does correspond to a melting transition. The
work with helium therefore has much more bearing on the question of the
existence of a two-dimensional solid phase than work with classical fluids.
Although there is some evidence from the specific heat measurements of
Stewart and Dash (1970) that films with very low coverage of helium atoms
382 J.M. KOSTERLITZ AND D.J. THOULESS [CH. 5,s 2

behave like quantum fluids, with specific heats proportional to T2for 4He and
T for 'He, there is no evidence for superfiuidity in monolayer films. Super-
fluidity can be observed in thin films a few atoms thick, and in such films there
appears to be a monolayer of helium atoms forming a solid on the substrate,
and superlluidity occurs above a layer which, according to Chester and Yang
(1973), is about 13 atoms thick. Experiments have been done on vycor
(Brewer and Mendelssohn 1961; Henkel et a]. 1969), which is a porous glass, on
grafoil (Herband Dash 1972) and on the surface of glass (Scholtz et al. 1974;
Telschow and Hallock 1976). Superfluid flow is detected in various ways,
which may either involve observation of mass transport under more or less
steady conditions or the observation of third sound in the film, which implies
the existence of a rapidly alternating supercurrent. Under these conditions the
superfiuid can be regarded as two-dimensional, since the coherence length is
much greater than the film thickness, so that the phase of the supeduid wave
function cannot vary appreciably between the substrate and the free surface
of the film. It is important that the surface of a piece of Pyrex is simple,
while in vycor there are multiple connections between the pores, since a
simple film might be regarded as more truly two-dimensional than a multiply
connected film and this influences what is observed (Berthold et a]. (1977).
The onset temperature at which superfluidity is observed is lower in helium
films than in the bulk, and decreases as the thickness is decreased. It is
not clear from the experiments whether the ideal transition is a sharp phase
transition or a more gradual quantitative change, since actual measurements
almost certainly involve averages over an inhomogeneous substrate with a
varying film thickness. One interesting feature of the results is that the super-
fluid density obtained from third sound measurements appeared to jump
discontinuously to zero, but this may have been a spurious effect due to the
large attenuation of third sound near the onset temperature (Scholtz et al.
1974; Telschow and Hallock 1976).
Specific heat measurements have also been made in the neighbourhood of
the transition. These also show a transition which occurs at a low temperature
in thinner films and a rounding of the transition so that the high peak of the
bulk specific heat becomes a low lump for films of five atomic layers or so
(Bretz 1973).
Between 2 mK and about 1 K bulk 'He behaves as a Fermi liquid, and the
nuclear spin enables a number of detailed measurements to be made by using
magnetic resonance techniques. In the same temperature range the solid is
paramagnetic. Measurements on 'He films have shown a strong enhance-
ment of the liquid magnetic susceptibility over the bulk susceptibility (Rolt
CH.5, S 21 TWO-DIMENSIONAL PHYSICS 383

and Brewer 1972; Ahonen et al. 1976). This seems to be due largely to the
solid-like layer of 'He atoms on the surface and the next high density layer
which are almost ferromagnetic and so enhance the paramagnetism of the
rest of the film (Beal-Moood and Doniach 1977). This interpretation is borne
out by the fact that a 4He impurity in the film, which goes preferentially to
the surface layer because of the higher mass of the atom, cuts down this
enhancement of the susceptibilityvery sharply.
For all cases in which some sort of phase transition appears to occur
the question arises of how far surfaces are homogeneous, and to what
extent the observed rounded peaks in specific heats are a result of an average
over different regions of the surface rather than a characteristic of a homo-
geneous film. This is a difficult question to answer, as most experiments
measure order over a rather short range. There is some discussion of this
problem in the book by Dash (1975).

2.3. TWO-DIMENSIONAL
ELECTRON GAS

Electrons can be trapped on surfaces in many different substances. In most

cases the surfaces are irregular and the electronic energy levels are dominated
by impurities, but in some cases surfaces are sufficientlyuniform that electrons
can move freely on them without being trapped, so that a two-dimensional
electron gas can be formed.
One example is the surface of liquid helium which is flat under the influence
of gravity except for the thermal motion and zero-point motion of surface
waves. Low energy electrons cannot penetrate into the helium, since the
p-band, which is the conduction band, is about a volt above the vacuum
level. Electrons are however attracted to the surface by their own image
charges, and so they are bound in a potential which is inversely proportional
to the distance from the surface, and are free to move parallel to the surface.
Since the dielectricconstant of liquid helium is close to unity the image charge
is small, and so the separation between the lowest level and the first excited
level (for fixed momentum parallel to the surface) is 0.55 meV. At sufficiently
low electron temperatures all the electrons will be in the lowest level, and a
two-dimensional electron gas will be formed; the coupling between the
electrons and the helium is quite weak, so the electrons can be at a higher
temperature than the helium. The interaction between electrons is inversely
proportional to distance at large distances, but is modified at short distances
both by the effect of the helium and by the finite extent of the wave function
in the perpendicular direction; both these effects c ~ t lbe altered by applying
3 84 J.M. KOSTERLITZ AND D.J. THOULESS [CH.5 , 8 2

an electrical field perpendicular to the surface to alter the shape of the wave-
function. It is necessary to compensate the long range repulsion between
electrons with a positively charged metal plate parallel to the surface, and it
is hard to get a high density on the surface, so that most of the effects observed
are due to the interaction of the electrons with helium rather than with other
electrons. There is a review of this subject by Cole (1974), and more recent
work has been reported by Grimes et al. (1976).
Experiments by Grimes and Adams (1976), have shown that the two-
dimensional plasma mode, with a frequency proportional to the square root
of wave number, exists, and its damping is due to scattering from surface
waves in the helium (Platzman and Beni 1976). It would be interesting to
observe the condensation of electrons to form a lattice at low temperatures,
but calculations by Hockney and Brown (1975) show that this should not
be expected at the temperatures and densities reached so far.
The Si-Si02 interfaces used in MOSFETs can also be made sufficiently
homogeneous to hold a two-dimensional electron gas. These are made by
growing a thin oxide layer on a cleared silicon surface, and a gate voltage is
then applied to a metal electrode on the other side of the oxide layer, as
shown in fig. 2. If the silicon is p-type a positive gate voltage is applied, and

tp-Si

Fig. 2. The layout of a MOSFET constructed from p-type silicon. The positive gate
voltage is applied to the metal electrode, and the surface current is passed between the two
n+ regions.

if this is saciently strong it will bend down the conduction band so that its
edge lies below the Fermi level, as shown in fig. 3. The electrons in this in-
version layer are bound to the surface, but can move more or less freely
parallel to it, and it can be arranged that the Fermi level lies above the lowest
level of the electron bound in this potential, but below the first excited state.
When motion parallel to the surface is taken into account the levels become
sub-bands, and the lowest sub-band will be partly occupied at very low
temperatures. On the (100) surface of silicon the effective mass is about 0.2
electron masses, the splitting between sub-bands is about 20 meV, and a
degenerate two-dimensional electron gas with a density of about lot6
electrons/m2 can be formed. The number of electrons can be controlled by
CH. 5,g 21 TWO-DIMENSIONAL PHYSICS 385

changing the gate voltage, which therefore changes the Fermi energy. Con-
duction in the inversion layer can be observed by using the two n+ regions
shown in fig. 2 as electrodes.
One of the most interesting features of the inversion layer is the low temper-
ature behaviour of the conductivity. Charges trapped in the oxide layer act
as scattering centres, so that the mean free path of the electrons is of the
order of 10 nm. When the wavelength becomes as large as this the electrons
are expected to become localized so that conductivity should be by activated
hopping, with energy supplied by the phonons; Mott (1969) has shown that
under these conditions the logarithm of the conductivity is proportional to

Acceptor levels

Fig. 3. The band structure in a ptype semiconductor when a voltage sutliciently strong
to produce an inversion layer is applied. The distance into the semiconductor from the
oxide surface i s denoted by z.

T - 1 / 3 .These localised states should occur at the bottom of the band, and
above some mobility edge the electrons should be in extended states (Mott
1966), and the conductivity should be independent of temperature at low
temperatures, as in a normal metal. It has been argued by Licciardello and
Thouless (1975) that the conductivity just above the mobility edge for any
system in which electron-electron interactions are not important should be
about 3 x ohm-'. All these features have been observed in experiments
carried out in Cambridge (Pepper et al. 1974; Mott et al. 1975; Adkins et al.
1976). There are however measurements on similar devices which give results
in conflict with these, both by Tsui and Allen (1974), and by Hartstein and
Fowler (1975). These results are due either to more significant effects from
electron-electron interactions or to greater macroscopic inhomogeneities in
the specimens. Measurements can also be made on many other properties,
such as magneto-resistive oscillations (Englert and Landwehr 1976) and ac
conductivity (Allen et al. 1975), which can be compared with theory (TZOW
et al. 1976).
386 J.M. KOSTERLITZ AND D.J. THOULESS [CH.5,s 2

2.4. SUPERCONDUCTIVITY
IN TWO DIMENSIONS

The arguments of Peierls (1934,1935) and of Hohenberg (1967) show that the
long-range order characteristic of a superconductor should not exist in two
dimensions, since the phase of the superconducting wave function has un-
bounded fluctuations, and the arguments of Kosterlitz and Thouless (1972)
show that a supercurrent should be unstable, since there is only a finite energy
barrier for the creation of a flux line. Nevertheless superconductivity is
observed in thin films under conditions in which the coherence length is much
greater than the film thickness, so that the behaviour is two-dimensional. This
subject is included in a recent review of fluctuation effects in superconductivity
by Skocpol and Tinkham (1975).
The theory of the superconducting transition in a thin film has been worked
out on the basis of Landau-Ginzburg theory by Ferrell and Schmidt (1967),
Abrahams and Woo (1968) and Schmid (1968), and on the basis of micro-
scopic theory by Aslamazov and Larkin (1968). In this theory there is an
enhancement of the conductivity above the critical temperature because of the
formation of small superconducting regions by thermal fluctuations. These
lead to a conductivityproportional to (T- Tc)-', with a coefficient that can be
calculated (Aslamazov and Larkin 1968). Measurements by Glover (1967) on
amorphous bismuth films, by Strongin et al. (1968) on dirty aluminium films
and by Smith, Serin and Abrahams (1968) on dirty lead films have confirmed
this prediction. The transition to the superconducting state appears to be
gradual, so that there is no temperature at which the conductivity suddenly
becomes infinite, although since the resistance drops exponentially as the
temperature is lowered it soon becomes unobservably small. There is a
critical region in which the transition from the (T-Tc)-' behaviour to the
exponential behaviour occurs. This is what would be expected from a theory
which denies the possibility of a sharp transition to superconductivity in two
dimensions,but may alternatively be a result of film inhomogeneities.
For clean films there is an additional effect which enhances the conductivity
predicted by Aslamazov and Larkin (1968) by a factor which is proportional
to ln(T-T,). This was calculated by Maki (1968) and by Thompson (1970,
1971), and been observed in a number of systems (Strongin et al. 1968; Crow
et al. 1970).

2.5. METALLIC
LAYER COMPOUNDS

Certain compounds, in particular the disulphides and diselenides of niobium

and tantalum, crystallizein such a way that the metal atoms form close-packed
ac 5.0 21 TWO-DIMENSIONAL PHYSICS 387

layers separated from one another by two layers of the nonmetallic atoms.
As a result the conduction electrons can move freely in the planes, but only
with difficulty between the planes, so that the conductivity in the parallel
direction can be greater by a factor of lo00 or so than the conductivity in the
perpendicular direction, and these materials can be regarded as two-dimen-
sional metals. The difference in conductivity in the two directions can be
further increased by intercalation of various organic materials between the
layers. Band structure calculations have been carried out by Mattheiss (1973)
and by other people, and have shown that the Fermi surface is almost
independent of the wave number component normal to the planes, so that the
electron velocity is almost parallel to the plane, and the dynamics can be
regarded as two dimensional.
These materials have a number of interesting phase transitions. There are
structural phase transitions involving a rearrangement of the close-packed
planes relative to one another or distortions of the planes. The materials can
become superconducting, thus giving another example of an almost two-
dimensional superconductor - however they are not truly two dimensional
since the phase of the order parameter is coupled between the layers by the
tunnelling of electrons from one layer to another. A particularly interesting
feature of these materials is that the electrons can form charge density waves
which may be either commensurate or incommensurate with the crystal
lattice. A review of this topic has been given by Wilson et al. (1975).
The types of transitions which occur depend on the basic type of crystal
structure of the compounds; the symmetry may be either octahedral or
trigonal prismatic, with various modifications. In the octahedral form (1T)
of TaSz there are two first order phase transitions at 352 K and 200 K, with
an increase in resistivity at each of them, so that at low temperatures the
material has a resistivity of the order of 10- ohmem, which is characteristic
of a semiconductor or semi-metal. The trigonal form (2m of TaSzhas a
second order phase transition at 80 K at which the resistivity begins to
decrease more rapidly, so that it reaches a value of lo-’ ohm-mat low temper-
atures. These resistivities are all measured parallel to the planes of metallic
atoms. X-ray and electron diffraction studies show that in the octahedral (1T)
forms the higher temperaturetransition corresponds to the establishment of an
incommensurate charge density wave with superlattice parameters that may
vary continuously with temperature. At the lower transition temperature the
charge density wave locks into the crystal lattice forming a commensurate
state. The lowered conductivity indicates that the charge density wave is
reducing the area of the Fermi surface to form something like a semi-metal.
388 J.M. KOSTERLITZ AND D.J. THOULESS [CH.5, g 2

In the trigonal(2H) forms the charge density wave does not occur until con-
siderably lower temperatures, and seems to be commensurate with the lattice.
Since conductivity increases the charge density wave is not reducing the
amount of Fermi surface available (Rice and Scott 1975).
One interesting point about the incommensurate charge density waves
observed with X-ray and electron scattering (Williams et al. 1976) is that
although one would expect the atoms to have Coulomb energies spanning
the entire range between the maximum and minimum of the potential
produced by the varying charge density, in fact X-ray photoemission exper-
iments seem to show only two different values for the atoms (Pollak and
Hughes 1976). This must mean that the sort of adjustment of the atoms
illustrated in fig. Id occurs.

2.6. MAGNETIC
LAYER COMPOUNDS

A survey of both experimental and theoretical aspects of magnetic layer

compounds is contained in the review by de Jongh and Miedema (1974).
These are materials in which the magnetic ions are arranged in planes such
that there is a strong coupling between the spins within a plane, but only a
weak coupling between spins in different planes. In materials such as FeCl,
and CoCl, there is a strong ferromagnetic coupling within the plane and a
coupling between planes which is weaker by a factor of 10 or so and anti-
ferromagnetic. In more complicated ferromagnetic layer compounds there
may be a greater distance between layers, and, for example, in (CH,NH,),
CuCl,, the interplanar coupling is down by a factor of more than a thousand.
There are many materials, such as Rb,MnF,, in which the coupling within
the plane is antiferromagnetic. This can result in a very much reduced coupling
between the planes, since one spin may have four spins in the next plane which
are at an equal distance, and their effects tend to cancel out. As a result the
coupling between layers in this material is down by a factor of lo6. The
sublattice magnetization of this material has been studied by Birgenau et al.
(1970a) using neutron diffraction and at lower temperatures using nuclear
magnetic resonance by De Wijn et al. (1971). The exponent j? relating the
sublattice magnetization to T,-T comes out to be about 0.18, which is a
fairly typical value for antiferromagnetic layer compounds, considerably
higher than the value 0.125 known for the two-dimensional Ising model, but
lower than values obtained in three-dimensional systems. The measured
anisotropy of the interaction is quite small, but it may have an important
determining effect in the critical region.
CH.5.5 31 TWO-DIMENSIONAL PHYSICS 389

Materials such as Rb,CoF4 and K,CoF, are strongly anisotropic anti-

ferromagnets which behave like Ising systems. The susceptibility of these
materials has been investigated in detail by Breed et al. (1969). The results
with these materials are in good accord with the calculations for the two-
dimensionalIsing model made by Sykes and Fisher (1962).
There has been an extensive investigation of layered copper compounds
such as (CnH2n+lNH3)2CuC14 which has been analysed by Bloembergen
(1975) to find out how an ideal Heisenbergferromagnetbehaves. By increasing
the value of n the strength of the interlayer coupling can be reduced, and the
results extrapolated to zero coupling. The critical temperature inferred for
this system is quite low, and could possibly be zero.
In these layered compounds the behaviour is only two-dimensional a
certain distance away from the critical temperature. Close to the critical
temperature there is a long-range correlation of the spins within the layer,
and such correlated regions will interact between one layer and the next even
if the coupling between individual spins is weak, since many spins can con-
tribute coherently. This is a similar situation to that mentioned for the super-
conductivity of layered compounds.

2.7. SMECTIC
LIQUID CRYSTALS

In the smectic phases of liquid crystals the molecules are arranged in regularly
spaced parallel planes. These planes can slip more or less freely over one
another, so that each plane of molecules is behaving in some sense like a two-
dimensional system. In the smectic A phase the molecules are irregularly
arranged in the plane, as in a two-dimensional liquid, while in the smectic B
phase there is a solid arrangement within the plane, although the positions of
atoms in different planes are not strongly correlated. DeGennes (1974) has
discussed the problem of whether the B phase is really a sort of three-dimen-
sional crystal, or if the layers are really free to move across one another as if
they were uncorrelated two-dimensional crystals, and he favours the former
possibility.

3. Phase transitions in two dimensions

3.1. INTRODUCTION

As discussed in the previous section there are a number of systems which are
quasi two-dimensional which can be realised experimentally. The problem of
B
390 J.M. KOSTERLITZ AND D.J. THOULESS [CH.5,# 3

phase transitions in two dimensions is not just a theoretical one. Of course,

real systems are never purely two dimensional because they either are coupled
together as in layered magnets or to a substrate as in thin films adsorbed on a
surface. To have a description of such a system, theory must take the effect
of this coupling into account or show that it is negligible. Not too much is
known about this at present but as we shall see even the weakest interaction
can have dramatic effects, in certain cases completely obscuring the ideal two-
dimensionalbehaviour. However, before attempting to describe a real system,
we must understand how the ideal system behaves.
There are a number of two-dimensional models which undergo a phase
transition for which exact results exist. The best known of these is the famous
Lenz-Ising model which Onsager (1944) showed has a continuous phase
transition. Then there are the two-dimensional ferroelectric models (Lieb
and Wu 1972) which can be regarded as generalisations of the Ising model.
These models display a wide range of critical behaviour ranging from first to
infinite order transitions. The spherical model (Berlin and Kac 1952; Joyce
1972) can be solved in any number of dimensions and in two has no tran-
sition at finite temperature. We shall not discuss such models any further here.
We now turn to the problem of systems with an order parameter trans-
forming according to a continuous symmetry. From a theoretical point of
view there are two apparently conflicting pieces of evidence to be reconciled.
The first is that it can be rigorously shown that a magnetic system described
by a rotationally invariant Hamiltonian has no spontaneous magnetisation in
two dimensions (Mermin and Wagner 1966; Mermin 1967) and the second is
the numerical results from high temperature series expansions (Stanley and
Kaplan 1966, 1967; Stanley 1967, 1968a; Ritchie and Fisher 1973; Moore
1969; Betts et al. 1971)which indicate a transition at a finite temperature. The
evidence for such a transition is somewhat better for the planar rotator model
(spins confined to a plane) than for the Heisenberg model. Low temperature
expansions (Berezinskii 1970, 1972; Wegner 1967) give a magnetisation
proportional to some power of the applied magnetic field between zero and
unity and indicate the possibility of a sharp transition between such
behaviour and the high temperature regime where the magnetisation is pro-
portional to the field. The limit of the number of components going to infinity
corresponds to the spherical model (Stanley 1968b; Kac 1971) which has no
transition (except at zero temperature).
Thus, two-dimensionalmodels range from Ising-like which have a transition
at finite temperature to the spherical model which does not. One of the tasks
of theory is to explain what happens in models between these extremes and
CH.$ 9 31 TWO-DIMENSIONAL PHYSICS 391

especially to elucidate the nature of a transition in which there is no spon-

taneous magnetisation in the low temperature phase. It must also be able to
answer the question: is there a special value of the number of components of
the spin below which there is a transition at finite temperature or is the
critical temperature just a decreasing function of the number of components
which goes to zero in the sphericalmodel limit?

3.2. MAGNETIC
SYSTEMS

We will restrict our discussion to classical systems for simplicity, although at

very low temperatures quantum effects will be important in real systems. It has
been shown that in certain models classical behaviour holds provided one
is sufficiently close to the critical temperature (Hertz 1976). We will assume
that the classical approximation is adequate to describe the behaviour of real
systems in two dimensions. With this simplification in mind we consider a
system on a hypercubiclattice in ddimensions with Hamiltonian

H = -3 J(lr-r’l)s(r)-s(r’),
r, r’

.;
where s(r) = (si(r), s2(r), . ,s,(r)) is an n-component spin of unit length at a
lattice site r, such that c:=i
s,’(r) = 1. We shall restrict ourselves to ferro-
magnetic nearest neighbour interactions and approximate the Hamiltonian by

H = ++Jdr(c7~)~. (3.2)
The motivation for such a continuum approximation is that the existence of
an ordered state is determined by the long wavelength fluctuationswhen only
spin configurationswith neighbouring spins differing infinitesimallyfrom each
other need be considered.
As an example, let us consider the planar rotator (n = 2) model in two
dimensions. We may parametrise s(r) by the angle +(r) it makes with some
arbitrary axis, so that the partition function becomes

Z = j64 exp {-(1/2T)j dr(v#2), (3.3)

where the temperature Tis in units of J/kB.Ignoring the fact that the original
Hamiltonian of eq. (3.1) is periodic with period 27r, the partition function
may be trivially evaluated. For example, the two-point correlation function is
392 J.M. KOSTERLITZ AND D.J. THOULESS [CH. 5,g 3

for all values of T. This implies that there is no phase transition in this model
and the spontaneous magnetisation is zero for all finite temperatures, in
accord with the Mermin-Wagner (1966) theorem. However, the power law
decay of the correlation function is not what we expect in the high temperature
regime. Moreover, the susceptibility is infinite for T < 8.n. This leads us to
suspect that although the approximations we have made are very plausible,
they are an over-simplification.
The model described by eq. (3.2) is not soluble for general n because of the
restriction Is(r)l = 1, except in the limit n + 00 when it becomes equivalent
to the spherical model. Recently Polyakov (1975) has applied renormalisation
group techniques to such systems near two dimensions. By exploiting the
ideas of Berezinskii and Blank (1973) he developed a method of successively
averaging out the short wavelength components of the spins in the spirit of
Wilson (1974) while maintaining the restriction of unit length spins at each
stage. Since the original work of Polyakov there have been a number of
papers on the subject using different techniques and approximations (Migdal
1975; Kadanoff 1976; Brezin andZinn-Justin 1976a, b; Brezin et al. 1976; Amit
and Ma). Brezin and co-workers have studied this problem by field theoretic
techniques. They prove renormalisability of such theories in 2+ e dimensions
thereby proving the scaling form of the thermodynamic quantities in the
asymptotic critical regime, and derive approximate forms for the scaling
functions. To leading order, the results are the same as Polyakov’s and the
difficulties are also similar.
Since Polyakov’s method is physically more obvious we will use this rather
than field theoretic methods to construct the renormalisation group procedure
for an isotropic system with the Hamiltonian of eq. (3.2). We take a hyper-
spherical Brillouin zone so that s(r) contains Fourier components sp with
I q1 < A, where A is a cut-off of the order of an inverse lattice spacing.
Berezinskii and Blank (1973) have shown that one can decompose s(r) into
short and long wavelength parts as

where s’(r) is a slowly varying vector with Fourier components 0 < I q1 <if’
and Is‘I = 1. The vectors {s’(r), e,(r), ..., en-l ( r ) } form an orthonormal
basis at each point in space and all the rapid variations are in the 4,(r) which
x
have Fourier components < I qI < A, and +’(r) = c::: 4,”(r). The e,(r)
are to a large degree arbitrary which we eliminate by the choice (Berezinskii
CH.5.8 31 TWO-DIMENSIONAL PHYSICS 393

and Blank f973)

Ve, = s'(e; Vs'). (3.6)

Using eqs. (3.5) and (3.6), the Hamiltonian becomes

Choosing the new cut-off /r = A(l -N) we can average over the 4s: by
perturbation theory in the calculation of the partition function

2 = Trs, Tr+ exp( -H/T). (3.8)

We find

Finally, we rescale the momenta q -,q(l +61) so that the range of q is

restored to its original value and, since Is'(r)l = 1, s'(r) is dimensionless so
+
that we must also rescale si + (1 dS1)si.After performing these calculations,
we obtain an effective Hamiltonian of the same form as the original one and
a rescaled temperature according to

dT/dl = -(d-2)T+ (n-2)T2/2~. (3.10)

This procedure generates a systematic expansion in d-2 and T,so that,

provided the critical temperature is small, it will give us a good approximation
in the low temperature ordered phase. From eq. (3.10) we see that there are
two fixed points

T* = 0
T" = 2n(d-2)/(n-2). (3.1 1)

The T = 0 fixed point is stable with eigenvalue 1, = -(d-2) and the other
is unstable with eigenvalue 1, = d-2+0(d-2)2. We identify this as the
critical point T, = T*, below which temperature there will be a non-zero
magnetisation (Polyakov 1975; Brezin and Zinn-Justin 1976a). From eqs.
(3.10) and (3.11) we see that provided, n > 2 and (d-2) < 1, T, is small and
394 J.M. KOSTERLITZ AND D.J. THOULESS [a.3 5 9 9

so this procedure provides a reasonable approximation in the low temperature

regime.
Unfortunately, these techniques do not allow us to extrapolate far into
the zero field, high temperature regime because we have made the implicit
assumption that we are in the ordered phase. When we try to use these re-
cursion relations for the disordered phase (T > T,) we find the solution

TJT(1) = 1 - (1 - T,/T) exp (d- 2)l (3.12)

which clearly is nonsense when exp (d-2)l > (1 -T0/T)-’ since we expect
that in an exact treatment as 1 + a,T(1) a.
This problem is especially acute in two dimensions when the recursion
relation becomes

dT/dl = (n-2)T2/2n, (3.13)

which has only one unstable fixed point at T = 0 and has the solution

T(1) = T(l -T(n-2)1/2~)-’, (3.14)

which again breaks down at 1 N 2n/(n-2)Te This does, however, show that
there is no spontaneous magnetisation at any finite temperature in agreement
with the Mermin-Wagner theorem.
These considerations allow us to define a characteristic length scale - the
correlation length

r(T) N ll-T/Tcl-1’(d-2) d>2

N exp[2n/(n-2)Tl d=2 (3.15)

and homogeneity relation for the momentum dependent susceptibility

(Pelcovitz and Nelson 1976)

(3.16)

which implies the scaling laws for the susceptibility

x(T) - t2-q

withq = T,/2n.
CH.5 , s 31 TWO-DIMENSIONAL PHYSICS 395

Unfortunately one cannot push the calculations much further at present.

All a renormalisation group transformation does is to relate a thermodynamic
quantity calculated from the physical Hamiltonian H,, to one calculated from
the effective Hamiltonian H(1). The hope is that one can do the calculations
with H(1) by more conventional techniques (perturbation theory, high tem-
perature expansions etc.), thereby deducing the physical quantity as in eq.
(3.16).We can compute x(T(I), qe') when qe' is large, but not in the disordered
phase for small qe'. This is equivalent to saying that we can calculate the two
point correlation function (s(r).s(O))when r/< < 1 but not when r/( > 1.
If the high temperature phase is truly disordered in the sense that there are
no Goldstone-like excitations (spin-waves), the correlation function should
r,
fall off as exp{-r/r} for r B but we cannot prove this by these methods
(see, however, Fisher and Nelson 1977).
This technique therefore does not prove that there is not another phase
transition at a temperature T > T,, and in particular that the Heisenberg
model in two dimensions does not have a phase transition. It is, however,
difficult to imagine what the broken symmetry phase would be if this were
not true. In the following, we shall assume that for n > 2 there is no transition
in two dimensions. This is supported by other arguments (Kosterlitz and
Thouless 1973).

3.3. THEPLANAR ROTATOR CASE* - TOPOLOGICAL ORDFB

When n = 2, the situation is somewhat different because then eq. (3.10)reads

dT/dl = -(d-2)T (3.17)

which, in this approximation, implies that T, = co. In two dimensions the

temperature does not change on iteration, but according to eq. (3.4) the
correlation function falls off only as r - T / 2 nwhich is not characteristic of a
true disordered phase so this treatment cannot tell if this physically important
case has a transition or not. Two approximations were made: (i) we ignored
the fact that 4(r)varies only between 0 and 2w and (ii) more importantly, the
topology of the field is a circle. These approximations are also made in the
n > 2 case, but the curvature of the sphere can be detected locally and this is
done to some extent in the perturbative treatment of the Hamiltonian.
The possibility that the angle 4(r) goes through a multiple of 27r was
ignored in the previous formulation of the theory. For example, the con-
* See Kosterlitz 1974.
396 J.M. KOSTERLfiZ A N D D.J. THOULESS [CH.5,# 3

figuration shown in fig. 4a corresponds to a change of +2n, while that of

fig. 4b to a change of -2z. These are closely analogous to vortices in a
superfluid. One may readily calculate the energy of such a configuration in a
system of radius R. In the configuration of fig. 4a

ql(r) = rJrI c1 = 12,

(b)
Fig.4. Typical singular configurations with a phase change of (a) A d = +2n and
(b) A 4 = -28. The dots mark the position of the singularity.
CH.5, g 31 TWO-DIMENSIONAL PHYSICS 397

whence, with the Hamiltonian of eq. (3.2)

E = R log R / t + O ( l ) (3.18)

where z is the lattice spacing. The entropy of such a conliguration is log

R 2 / t 2 since its centre can be placed anywhere in the system, so that the free
energy is

AF = ( R - ~ Tlog
) Rlt. (3.19)

At sufficiently low temperatures (T-c +n) such singular configurations are

forbidden, while at high temperatures (T > 3). they can be thermally
activated, thus increasing the disorder of the system. Of course, there are
fluctuations about such configurations and also pairs of singularities of
opposite strengths which have a finite energy proportional to the logarithm
of their separation.
This leads us to the concept of topological order (Kosterlitz and Thouless
1972, 1973) whose presence or absence may be determined in the following
manner. The total change of phase on going round a large closed path in the
system will be determined by the number and strength of the singular points
enclosed by the path. Thus, if there are isolated singularities present (high
temperature regime), the number of these will be proportional to the area
enclosed by the path. The average total phase change will be proportional to
the length L of the contour. If, on the other hand, only pairs of singular points
are present (low temperature regime), the total average phase change will be
determined by the number of pairs cut by the path, and so will be proportional
to (Ld)’’’ where dis the mean separation of pairs.
Now consider a large system with periodic boundary conditions. The
number of multiples of 2n by which the phase changes on a path going right
round the system is a topological invariant so that

are numbers defining a particular state. Transitions between one state and
another take place if a pair of singularities is formed, and recombine after one
has gone right round the system, which will cause a change of one in either
n, or ny. There is, however, a logarithmically large energy barrier which can
be only overcome at sufficiently high temperatures.
398 J.M. KOSTERLITZ AND D.J. THOULESS [CH. 5 , s 3

-
It is straightforward to show that for a power law interaction of the form
J(r) r - ( z + O J the energy of an isolated singularity is proportional to log R/z
when Q > 2, and the same arguments will hold, except that the critical value
of Twill be changed. For 0 < Q < 2 the energy is proportional to (R/z)'-" so
that such configurationscan be ignored.
For the two-dimensional Heisenberg model, on the other hand, there is
only one topological invariant (Kosterlitz and Thouless 1973), but the energy
barrier for changing this is of order unity and so transitions can take place at
any finite temperature. This supports the assumption of the previous section
that there is no transition in this case.
Now we will try to put these ideas on a more formal and detailed basis
following the ideas of Toulouse and Klkman (1976) who discuss the classifi-
cation of topologically stable defects. They show that in a system with an
order parameter described by an n-component unit vector there are topologi-
cally stable singular configurations (defects) which have a surface of singu-
larities of dimension d-n, where d is the spatial dimension of the system.
There are many well known examples of this in physics - vortices in superfluid
4He, disclinations in nematic liquid crystals (DeGennes 1974), disclinations
and dislocations in crystals (Friedel 1964; Nabarro 1967) and many more.
An example equally well known but less obvious when looked at from this
point of view is the king model. The only way of making deviations from the
completely ordered state is to flip blocks of spins. The boundaries between the
domains of spins of opposite orientation are the defects-points in one dimen-
sion, lines in two, and surfaces in three. By specifying aparticular configuration
of defects one specifies the configuration of spins, and so, knowing the energy
of the defect configurations, one can,in principle, do the statistical mechanics
of the Ising model.
There are two separate problems to solve before attempting the statistical
mechanics, (i) the classification of the possible types of defect, which depends
only on the topology and (ii) the energy of a specified configuration of defects
which depends not only on the number and types of defect present but also
on the particular Hamiltonian of the system. The latter problem is much the
harder. As an example, let us consider a one dimensional Ising system with a
Hamiltonian

(3.20)

which has a trivial topology. Imposing cyclic boundary conditions, the spin
configuration is completely determined by the 2N point defects at rl , r z , ...,
CH.$ 9 31 TWO-DIMENSIONAL PHYSICS 399

r2N.It can be shown that the energy of such aconfiguration is

2N
E2N = E(r,-rj)+2Nfl~
i +I
where

E(r, -rj) = (-)‘+’[a(l -a)]-‘( Irl -rj I ’

-O- +
1) O(l ri-rj I -7 (3.21)

and fl is the ‘chemical potential’ of a defect. It is possible to do approximately

the statistical mechanics of this system using a renormalisation group pro-
cedure (Kosterlitz 1976; Anderson et al. 1970; Anderson and Yuval 1971)
but this is not the point here. We merely wished to illustrate that one can have
a trivial topology but the energetics can be difficult.
Returning to the planar rotator case in two dimensions, because n = d we
have topologically stable point defects (Toulouse and Kleman 1976) cor-
responding to typical spin configurations shown in fig. 4. A ‘topological
current’ can be defined (Patani et al. 1976)

whose divergence obeys (Patani et al. 1976)

j y ddr a,,j, = Nad,

where N is an integer and adthe surface area of a d-dimensional unit sphere.

This implies that a, j , has &function singularities

a,j, = ad C1 n, &-3, (3.23)

where n, is an integer (the strength of the defect at rJ. Equation (3.23) has
the solution

where J,(r) is a function of r such that aJ,, = 0. Up to now our discussion

has been general, valid for any unit vector order parameter with n = d. We
must now solve eq. (3.22) for J in terms o f j in order to write the Hamiltonian
in terms of the defects. This is not so straightforward, and to the authors’
knowledge has been solved only for the special cases of one and two dimen-
sions, which, fortunately, includes the case under discussion.
400 3.M. KOSTERLlTZ AND D.J. THOULESS [CH. 5,P 3

For n = d = 1, the solution is trivial with the expected result

Nr) = A 4 = Ci (-)%(r-ri). (3.25)

For n = d = 2 we can parametrise s(r) by an angle 4(r) whenj,,(r) = c,va,~(r)

and so

It is straightforward to see from eq. (3.24) that the Hamiltonian of eq. (3.26)
can be written as

H = H,+Ho, (3.27)

where H, is the part due to the defects and Ho describes the smooth fluctua-
tions about these. An explicit calculation taking into account the underlying
square lattice structure gives (Kosterlitz 1974)

where z is the lattice spacing and 2p N n2 is the energy of a configuration in

which two defects of strength & 1 are at one lattice spacing apart. The term
zii ninj log R / z imposes the restriction that nr = 0. Ho may be written

Ho = f 1(V$)'d2r (3.29)

where J/ is a single-valued field describing the deviations from the local

minima of energy H,. Note that a specification of the defects is insufficient to
completely describe the spins, since small fluctuations of the spins from their
positions shown in fig. 4 will not change the topology. The angle $ (r), which
obeys $d$(r) = 0, completes the description of the spin configurations.
In what follows we shall assume that only defects of unit strength are pre-
sent, since these are more favourable than those with n, 8-2. We have
investigated the effect of keeping more defects and this does not change the
qualitative aspects of the solution. In such a case, the partition function may
be written as (Kosterlitz 1974)
CH.5,431 TWO-DIMENSIONAL PHYSICS 401

where
Tr = Sa)O C “ --iI:2rI
1 ...d2rjN.
N=O (N!)

Since there must be N defects and N anti-defects for the condition n, = 0

to be obeyed, we must include the weight factor ( N ! ) - 2 . The domain of
integration is such that lri-r,l > T, since two defects cannot be less than a
lattice spacing apart. In this approximation, the partition function for the
magnetic system becomes exactly the grand partition function of a neutral
Coulomb plasma of 2N charged particles of diameter z. This finite short
distance cut-off prevents the collapse of pairs of oppositely charged particles
into an infinitely deep potential well (cf. Hauge and Hemmer 1971).
The treatment of this system by renormalisation group methods is des-
cribed in detail by Kosterlitz (1974), so we shall merely outline the procedure.
The cut-off, or lattice spacing is scaled to ~(1+62) and the pairs of defects
lying between z and z(l+61) are averaged out. This procedure reproduces a
Hamiltonian of the same form as eq. (3.28) but with rescaled parameters
(according to Kosterlitz 1974)

d(l/T)/dl = -4z312/T2 +O(A4)

dI/dl = -A(n/T- 2) +0(13), (3.31)

where I is the activity exp(-p/T) and eq. (3.31) is valid for small I. Various
irrelevant terms describing interactions between more than two defects are
generated by this procedure, but they do not affect the main results, and have
been ignored. Equations (3.31) have solutions as shown in fig. 5. The I = 0
axis is a fixed line which is stable for T < +z and unstable for T > +a.
We interpret this as follows. For T < T,, assuming that our initial
Hamiltonian is within the range of validity of eq. (3.31) (or that there are no
other fixed points inaccessible to our approximations), which implies that
ignoring defects of more than unit strength is not unreasonable, I will scale to
zero. Thus our system is equivalent to one in which there are no defects, and
the naive Gaussian form of the Hamiltonian is valid. For T > T,, the
opposite is true because eventually on iteration the activity increases and we
go outside the range of validity of the recursion relations. We interpret this
as indicating that we are in the disordered phase because a large number of
defects clearly corresponds to less order, provided, of course, there are no
other fked points except the one at T = GO.In this regime we come up against
402 J.M.KOSTERLITZ AND D.J. THOULESS [CH.5,s 3

exactly the same problems as those discussed previously (Polyakov 1975;

Brezin and Zinn-Justin 1976a).
Within the approximations outlined above, we find the following scaling
laws near the unstable fixed point T* = +n (Kosterlitz 1974):

(i) T, is the solution of

n/Tc-2 = 2n exp( -PIT,) +O(exp -2p/Tc); (3.32)

(ii) Correlation length

c(T)= 00 T<Tc
= exp a(T/Tc- 1)-lI2 T > T,; (3.33)

Fig. 5. Trajectories in the (l/T,d) plane of eqs. (3.1). The broken line indicates the physical
initial values of 1 = exp ( - p / T ) .

(iii) Susceptibility
x(T)= 00 T<Tc
- t2-" T > T, (3.34)

with q = 4. This is in disagreement with a recent calculation by Luther and

Scalapino (1977) who find q = 8-lI2;

(iv) Free energy

AT) - A, r 2+fo(T), (3.35)

where fo(T) is analytic at T,, This implies that the specific heat exponent
ct = -a,so that the specific heat is smooth at T,. We are unable to tell
whether there is a bump in the specific heat at T, or some other value of T.
In the F model, which also has a similar essential singularity in the free energy,
the specificheat has a maximum below T, (Lieb and Wu 1972).
CH.5, ij 31 TWO-DIMENSIONAL PHYSICS 403

(v) Correlation function

(s(r)*s(O)) - Irl-qfT) T < T, (3.36)

where q(T) N T/2n at low temperatures and as T + T,- we have q(T) N &
-C(l -T/T,)'''. This treatment is good only for T < T,,and we have not
been able to find the behaviour of the correlation function in the disordered
r,
phase when r % although, if there are no other fixed points, we expect it
to decay exponentially.
Of course this treatment can give only a very crude estimate of T, since we
have ignored terms in the initial Hamiltonian like ( etc., which would
arise from an expansion of si-sj = cos(4i-4,). Although such terms are
irrelevant and do not affect the asymptotic critical behaviour, they will affect
the value of T,. Villain (1975) has constructed a model in which the defect
+Gaussian form of the Hamiltonian is exact. He chooses an interaction
V(4) which keeps the important feature of the Hamiltonian, namely the
periodicity, and adjusts the coupling constant so that exp{A(T) V(+)} is as
good an approximation as possible to exp{cos+/T). Replacing 1/T by A ( T )
in eq. (3.32) he gets a T, which is in good agreement with the series expansion
estimates of Stanley and Kaplan (1966, 1967). Further evidence for the sus-
ceptibility of eq. (3.34) is provided by the work of Camp and Van Dyke (1975)
who re-analysed the high temperature series in terms of a susceptibility
behaving as exp{u(T/T, - l)-'} and find some support for such a form but
with v N 0.75. However, corrections to scaling are large which may explain
this discrepancy.
Zittartz (1976) has also looked at the two-dimensionalplanar rotator model

He finds a free energy in an external fieldf -I

from a different point of view, and reaches quite different conclusions from us.
hl K ( T ) with K(T)= 4/(4- q(T))
and he gives various estimates of K(T).The essential difference between his
results and ours is that he finds, on the basis of low temperature expansions,
the spin wave stiffness constant vanishesat a higher temperature than that when
q(T) = 4. At higher temperatures than this, he finds that all correlation
functions are finite so that one may assume that the free energy is analytic.
Thus, he identifies T, as the solution of q(T,) = 4. On the other hand, we find
that the spin-wave stiffness constant vanishes discontinuously at a much
lower temperature.

3.4. ANISOTROPIES
IN TWO-DIMENSIONAL MAGNETS

All real layered magnetic systems have both anisotropies within a plane due
404 J.M. KOSTERLITZ AND D.J. THOULESS [CH.5,O 3

to crystal field effects etc. and weak coupling between the planes. These have
very dramatic effects even for a ratio of interplanar to intraplanar couplings
lJl/JllI as low as which is about the lower limit for real systems. In fact
even such a small ratio can completely mask the critical behaviour of the ideal
two-dimensional system. The same holds true for anisotropies in the plane
where a ratio of anisotropy to exchange couplings of the same order of
magnitude can completely obscure the critical behaviour of the isotropic
system. Recent experiments on K,NiF4 and K,MnF4 (Birgenau et al. 1970b;
Als-Nielsen et al. 1976) bear this out. These are nearly ideal two-dimensional
Heisenberg antiferrornagnets in which there is a small Ising-like anisotropy
of about lo-’ JIIand an interplanar coupling JI N JII(de Jongh and
Miedema 1974). In the temperature range I T/T,-1I 2 lo-’ an order
parameter exponent fl II 0.138 is found (Birgenau et al. 1970b), although
Binder and Landau (1976) point out that, by shifting T,,the data is quite con-
sistent with the two-dimensional Ising value of 0.125. The staggered sus-
ceptibility exponent as measured by neutron scattering is consistent with the
Ising value of 1.75 (Als-Nielsen et al. 1976). Thus, despite the small magnitude
of the Ising anisotropy, behaviour characteristic of the two dimensional
Ising model is observed. This is in complete contrast to the situation in three
dimensions.
Pelcovitz and Nelson (1976) have investigated the effect of anisotropies
near two dimensions for Heisenberg-like models with the number of spin
components n > 3 by Polyakov’s (1975) technique. They consider a Hamil-
tonian with both Ising-like and cubic anisotropy

where oi denotes one of the components of si. They find that g2 and v are
strongly relevant with eigenvalues about the isotropic fixed point (eq. 3.1 1)
= 2, = 2 in two dimensions, while g, is marginally irrelevant. In the case
where there is no cubic anisotropy, v = 0, this means that the coefficient g,
of the o: terms grows very rapidly

Thus the effective Hamiltonian at the Zth stage of iteration has the same form
as eq. (3.37) but with a large coefficient g,(Z). If g, < 0, the minima of the
Hamiltonian are at oi = f l and so the system is equivalent to the Ising
CH.5,s 31 TWO-DIMENSIONAL PHYSICS 405

model. Similarly, if g , > 0, the system crosses over to rn = n- 1 behaviour.

Specialising now to n = 3, the combination g , exp(4n/T) is a renormalisation
group invariant, so according to conventional lore, the critical temperature
will be given by

(3.39)

where z, is some constant, This has the solution

where g , is the strength of the anisotropy measured in units of the isotropic

exchange coupling. Since the critical temperature of the two-dimensional
model is finite, then z, is also finite, but a more detailed analysis is necessary
to estimate its value. The same is true if g , > 0 since, according to the theory
of the previous section, the two dimensional planar rotator model also has
a finite T,.
The lower limit in real materials is g , N which means that the shift
in T,is fairly large since log lo6 is still rather small. To see the pure isotropic
Heisenberg critical behaviour two conditions must be simultaneously satisfied
(i) T must be sufficiently far from T,(g,) so that the effects of the anisotropy
are not felt too much and (ii) T must be close enough to T,(g, = 0) (which
is zero in this case) so that we are still in the critical region of the pure system.
For real materials, by virtue of eq. (3.40) these two conditions are impossible
to satisfy, and so we are unlikely to see pure two dimensional Heisenberg
behaviour. The same considerations hold for any relevant perturbation about
the isotropic system (cubic etc.). Since in two dimensions, there are an infinite
number of possible relevant perturbations (Brezin et al. 1976) (in contrast
to the situation near four dimensions (Zia and Wallace 1975; Wegner 1972a,b,
1974) a real system is almost certain to have one or more of these present
in the interaction due to crystal field effects etc.
Binder and Landau (1976) have recently tested these ideas by Monte Carlo
techniques and find consistency with the predictions T,(g2 = 0) = 0 and
T,(g2)cc [logg,I-', although their data does not rule out a non-zero
T,(g, = 0), and then they find consistency with a more conventional form

with Q N 4. Assuming power law behaviour for the susceptibility and specific
heat they find the ideal two dimensional Heisenberg exponents yH = 3,
406 J.M. KOSTERLITZ AND D.J. THOULESS [CH. 5,$3

aH N -2, which are similar to the high temperature series estimates, (Stanley
1967, 1968a; Ritchie and Fisher 1973; Moore 1969) but their data are also
consistent with an exponential susceptibility. In the presence of an Ising
anisotropy, a two-dimensional Ising exponent of 1.75 is observed close to
T,(g,) and a yclf N 2.2 further above T,. These results are not surprising if
one considers the following simple picture. Suppose the ideal isotropic
susceptibility behaves exponentially so that the effective exponent yerr(T)N
4n[T-T,(g,)]/T2 for T % T,. This must match on to the value yerr(Tc)= 1.75.
Thus, the effective exponent will rise to a maximum value ymaxat some tem-
perature above T, and then fall to its Ising value. The susceptibility data will
have approximately the same slope, when plotted logarithmically, over the
largest range of temperature, when yerr(T)= ymax.Thus, the data will appear
to predict a definite value of ycft outside the Ising-like critical region.
The situation in layered magnetic systems is even worse because there will
not only be anisotropies within the plane which are themselves sufficient to
obscure pure isotropic behaviour, but also the interplanar coupling JL which
is at least 10-6J,lin real materials. It can be generally shown (Liu and Stanley
1972, 1973) that the exponent for cross-over from two to three dimensions is
equal to the two-dimensional susceptibility exponent y. Thus, in purely
isotropic exchange coupled layered Heisenberg magnets (n > 3), the inter-
planar couplingJLwill grow on iteration like

(3.41)

Using the same arguments as for anisotropies in the plane, the critical tem-
perature is shifted to

,the intraplanar
where x, is a finite constant and JL is measured in units of JII
coupling. This form is verified in the spherical model where (Joyce 1972)

Tc(JJ = n{log (32/JJ} -I. (3.43)

These results imply again that one is unlikely ever to see isotropic two-
dimensional critical behaviour experimentally. It is also likely that attempts
(Bloembergen 1975) to estimate the ideal two-dimensional critical temperature
from experiments on layered systems are doomed to failure at least until
theoreticians produce a more detailed theory of layered systems, including
CH.5 , # 31 TWO-DIMENSIONALPHYSICS 407

both interplanar couplings and spin anisotropies, capable of predicting the

functional form of the measured thermodynamicquantities.
If the Ising anisotropy is much greater than the interplanar coupling, on the
other hand, the two-dimensional behaviour will be Ising-like and the shift
in T, due to Jl will be small

T,(Jl) -T,(O) N JI",

which is small since 4 = 1.75. Thus the two-dimensional Ising behaviour will
be observed, as it is in K2NiF4 and K,MnF4 (Birgenau et al. 1970b; Als-
Nielsen 1976), before the final cross-over to three-dimensional behaviour
very close to T, .
So far our discussion has been limited to Heisenberg models with n 2 3.
The exceptionalcase of n = 2 has been studied by several authors (Pokrovsky
and Uimin 1973, 1974; Berezinskii and Blank 1973*) in the low temperature
region where the Gaussian approximation of eq. (3.3) to the Hamiltonian is
valid. Consider the Hamiltonian

H = 3 (84)2d2r+hp cosp4(r)d2r, (3.44)

where the anisotropy cosp4 corresponds to a uniform magnetic field (p = l),

an Ising ( p = 2), a cubic anisotropy (p = 4) etc. In the low temperature
region, ignoring the effects of defects, for small h, we have (Berezinskii and
Blank 1973; Birgenau et al. 1970b)

where

1, = 2-p2T/4~,

If we take the defects into account this is modified to

(3.46)

which can readily be derived by the methods of Kosterlitz (1974), with

q(T) N T/2n for low temperatures and q(T) N a-C(T,-T)''2 for T N T,.

* Note that these authors are correct only in the n = 2 case because they omitted to take
into account the rescalingof the temperaturefor n 3 3.
408 J.M.KOSTERLITZ AND D.J. THOULESS [CH. 5,g 3

Since q(T,) = t , for p < 4 such a perturbation is relevant at the critical

temperature of the pure isotropic model and so the system will cross over to
some other critical behaviour - for p = 2 to Ising and p = 3 to the three-
state Potts (1952) model. For p = 4 (cubic anisotropy) the perturbation is
relevant below T,(h, = 0) and marginal at T,(O). It is not clear to what the
system crosses over in this case, but when h4 is very large the system reduces to
two Ising models with a coupling which vanishes as h4 -+ 00 which is very
similar to that of the Ashkin-Teller model (Ashkin and Teller 1973; Kadanoff
and Wegner 1971). Forp > 4, on the other hand, the perturbation is relevant
for T ;5 16T,/p2 and irrelevant for 1 > T/T, > 16/p2.Thus there should be
two transitions in such a system. At T N T,(O) there will be a transition of the
type discussed in 0 3.3, with no spontaneous magnetisation but an infinite
susceptibility, and at a lower temperature T,, N 8x1~'another transition to a
phase in which there is a non-zero spontaneous magnetisation. It is amusing
to speculate that traces of this low temperature transition may be detectable
in layered systems with the appropriate symmetry.
The effects of an interplanar coupling JLon an isotropic n = 2 system are
almost as dramatic as for n > 3. By the same arguments as we used before, it
can easily be shown that

(3.47)

where z, is a finite constant and a is the constant which appears in eq. (3.33).
An Ising-like anisotropy in the plane will lead to a shift in T, of the same form
as eq. (3.47). Since the shifts in T, are large for realistic values of the aniso-
tropy, the same pessimistic conclusions hold in this case as for the Heisenberg
case. To conclude, in any real layered magnet, one is faced with a triple cross-
over phenomenon to analyse (de Jongh and Stanley 1976) since interplanar
couplings and anisotropies as small as make themselves felt in a dramatic
way. This leads the authors to think that, except in the Ising case, an analysis
of experiments in the critical region in terms of exponents is not a fruitful
approach but that the data should be fitted to some, as yet, non-existent
functional form for the quantity under investigation.

3.5. SUPERFLUIDS

Superfluidity in thin films of 4He is now well established, so one runs up

against the same sort of problem as in the two-dimensional planar model, but
in a more acute form. One could argue in the magnetic case that it is the
CH.5,s 31 TWO-DLMENSIONAL PHYSICS 409

coupling between the layers in a real system which is responsible for the
observed finite critical temperature, as theory predicts for the Heisenberg
model. Superfluidity is observed in films about two atomic layers thick
(Scholtz et al. 1974), which is as close to a two-dimensional system as it is
possible to get. However, Hohenberg (1967) showed that for a two-dimensional
Bose fluid, off-diagonal long-range order (Penrose and Onsager 1956) does
not exist in the thermodynamic limit. Thus, if one insists that long-range
order is essentialfor superfluidity,one has to look for other ways out.
One possibility that has received a lot of attention (Imry 1969; Jasnow
and Fisher 1969,1971) is that, although the theorem is rigorous in the thermo-
dynamic limit, real systems are finite in extent and so a Bose-Einstein con-
densation might still take place. In the ideal Bose gas one finds a macro-
scopically occupied state for

T < T,(A) cy T3/10g Ad, (3.48)

where d is the thickness of the film, A the area of the system and T3the con-
densation temperature of the bulk. As the area A * 00, T,(A) + 0 consistent
with the Bogolyubov inequality (Hohenberg 1967). However, for a realistic
system, log Adis not very large, and so Bose-Einstein condensationis possible.
The methods of Hohenberg (1967) have been extended to finite systems in
which one dimension is small (Jasnow and Fisher 1969, 1971), and upper
bounds established for a quantity analogous to the condensate fraction

where 4 is a slowly varying function of density p, temperature T and film

thickness d. This again implies the possibility of having condensation in a
large but finite region.
A second way out along these lines is to argue that, since the film of 4He is
adsorbed on a substrate, it is possible that inhomogeneities of the substrate
cause spatial variations of the single particle energies. It has been shown that
for certain forms of the spatial variation, Bose-Einstein condensation in an
otherwiseideal Bose gas of infinite area can take place (Dash 1975).
A third approach (Berezinskii 1972; Kosterlitz and Thouless 1973;
Kosterlitz 1974) is to take the point of view adopted in 8 3.3 and ask the
question - is superfluidity possible without long-range order? Let us suppose
the condensation occurs in small regions of the system so that a condensate
wave function can be defined
410 J.M. KOSTERLITZ AND D.J. THOULESS [CH.$ 0 3

+(r) = I +(r)l ei+('). (3.50)

Provided the length scale of spatial variations of the condensate wave function
is sufficiently large, one should be able to write down a Ginzburg-Landau
free energy functional to describe the system near T,,and so we will arrive at
an effective Hamiltonian of the form

We assume that we are well below the mean field temperature, so that
r,(T) -+ 0 and fluctuations in the amplitude I $1 will be small. These assump-
tions are supported by some recent work of Amit and Ma who showed that
'
for n > 2 (Is1 - 1) is an irrelevant operator whose coefficient has a fixed
point value of infinity in two dimensions, so that amplitude fluctuations are
damped out on iteration. If the above assumptions are valid, the Hamiltonian
for a two-dimensional Bose fluid can be written in an equivalent form to the
planar rotator

H = h2n(r)/2m j(Vc$)'d2r, (3.52)

where m is the effective mass of a helium atom and n(T)is the effectivenumber
density of helium in the film. Berezinskii (1972) has derived a lattice gas
description of a two-dimensional Bose fluid which is equivalent to eq. (3.52).
Note that superfluid density p,(T) is equivalent to the spin-wave stiffness
constant of a magnetic system, and may be defined as (Hohenberg and
Martin 1965; Halperin and Hohenberg 1969a,b)

If the naive Gaussian form of the Hamiltonian of eq. (3.52) is used, ignoring
any possible singular configurations

as expected.
The singular configurations in this case are the usual vortices in 4He, which
in a two-dimensional system are defined by their position r , and vorticity n,.
Exactly the same arguments as for the magnetic system may be used. The
energy of an isolated vortex in a system of radius R is (nh2n(T)/m)log (R/T),
so that the critical temperature is approximately nh2n(T)/2m.So, at sufficiently
 CH.5 , i 31 TWO-DIMENSIONAL PHYSICS 411

low temperatures there will be no free vortices, only clusters of zero total
vorticity and the system will show the characteristics of a superfluid, although
there is no long-range order in the usual sense.
If interactions between the vortices are taken into account, the critical
temperature is lowered to

nhZn(T,)/2mT,- 1 N 2n exp( -p/T,),

where p is the vortex core energy. The superfluid density as defined by eq.
(3.53) can be shown to behave close to T, as (see fig. 6 )

(3.55)

Fig. 6. The superfluid density p,(T) for a two-dimensional superfluid. Note the dis-
continuous drop to zero at To.

Note that p,(T,) is finite, so we predict that the superfluid density goes to zero
discontinuously at T,.This is consistent with any scaling theory such as that
based on the concept of a helicity modulus (Fisher et al. 1973)and does not
mean that the transition is first order.
The vortex model as formulated above predicts that the superfluid onset
temperature and coverage are related by

(n,)d/T, N 2m/(nh2b)N 15 x 10’’ cm-’ K-’,

where d is the thickness of the film measured in layers, each layer being
b N 3.6 A thick, and m is the mass of a 4He atom. (n,) is the average super-
fluid number density in the film. The experimental data seem to support a
thickness versus onset temperature law of this form, but the experimental
412 J.M. KOSTERLITZ A N D D.J. THOULESS [CH. 5,g 3

situation is still confused (Dash 1975). There is some disagreement in the

interpretation of the average superfluid density (n,) (Padmore and Reppy
1973) and also the thickness d is presumably not completely uniform across
the film due to substrate inhomogeneities (Dash and Herb 1973; Cole et al.
1975). Also the measured superfluid density will depend on the experimental
technique. For example an experiment carried out at a finite frequency at
fixed temperature shows that the apparent critical coverage decreases with
increasingfrequency (Dash 1975; Chester et al. 1972; Chester and Yang 1973).
A theory has recently been proposed (Dash and Herb 1973) to explain these
variations - the connectivity theory, which exploits the substrate inhomo-
geneities. The similarity of most adsorption isotherms for different substrates
is normally taken as an indication that the effects of heterogeneity are healed
out as the thickness of the film is increased. However, this is not necessarily
true if the thickness of the film is small compared to the scale of lateral
variations of the binding energy to the substrate (Cole et al. 1975). In such a
situation, it is argued that, because the vapour pressure must be constant over
the film, the thickness dand the binding energy a are related

6d/d cc 6a/a.

Thus the thicker the film, the greater the variations in thickness. When,
however, the thickness is larger than the lateral scale of inhomogeneities the
film thickness becomes more uniform.
On an inhomogeneous substrate, there will be pools of thicker film which
will be the first to become superfluid, and so the onset temperature will be
technique dependent. In a quartz crystal microbalance type of experiment
(Chester et al. 1972) which is carried out at a frequencyfin the megacycle
range, superfluidity will be felt when the characteristic size of the pools of
thicker film is of the order of the third sound wavelength at the given fre-
quencyf, so that onset will depend on the frequency. There is still some
controversy about this theory (Chester and Yang 1974).
There is an alternative explanation of the increase in onset temperature
with frequency which does not require inhomogeneity of the substrate.
Suppose that in a uniform film, the superfluid velocity decays exponentially
u&) N exp( -t/z(T)) where T(T)is a relaxation time for T > T,,and a much
slower decay for T < T,. Superfluid flow must decay even below T,owing to
the presence of vortices (Langer and Reppy 1970). During each cycle, a flow
relative to the substrate is induced and provided the relaxation time r(T) > l/f
a superfluid-like response will be seen and will have the observed frequency
CH.5 , # 31 TWO-DIMENSIONAL PHYSICS 413

dependence. Also the apparent superfluiddensity will go continuouslyto zero,

instead of discontinuouslyas in eq. (3.55).
The true explanation probably lies somewhere between the two, but almost
certainly substrate inhomogeneitiesare important in very thin films. There are
many problems still outstanding in thin films. The theory of dynamics near
onset is still an open one and an obvious problem is the anomalously high
attenuation of third sound near onset. It is interesting to speculate that this
may be due to vortices in the film.

3.6. CRYSTALLINE ORDER IN TWO DIMENSIONS

We now turn to the problem of two-dimensional crystalline order and the

melting transition. This has been observed in a number of gases adsorbed
on various substrates. The structure of the adsorbed gas has been directly
observed for certain combinations of gas and substrate by LEED and neutron
diffraction (Dash 1975). For example for N2monolayers on graphite (Kjems
et al. 1976) the measurements indicate that at high temperature (T> 78 K)
there is short-range but no long-range order at low and high coverages. At
intermediate densities a triangular lattice in registry with the substrate
(a 1/3 x 4 3 epitaxial structure, Dash 1975) is observed, while at higher
coverages and low temperatures a close packed triangular lattice not in
registry with the substrate is also observed, with a lattice spacing very close
.
to that of (1 11) planes in solid bulk Nz The data is consistent with a con-
tinuous transition to a liquid or gaseous state. No direct observations of the
structure of 3He and 4He monolayers on various substrates have been made,
but by comparison with the Nz observations, the specific heat data can be
interpreted to indicate that at intermediate coverages on graphite there is a
43 x 1/ 3 epitaxial phase, and at near monolayer completion there is an
ordered triangular crystal not in registry with the substrate.
We will discuss the theory of the high density unregistered monolayer
under the assumption that the substrate provides a uniform binding potential.
Effects of the periodicity of the binding potential on the melting transition are
not taken into account. This seems to be a reasonable approximation except
at coverages very close to monolayer completion when additional compli-
cations arise due to promotion of some atoms to the next layer and vapour
(Elgin and Goodstein 1973, 1974). The low temperature specific heat of such
layers follows the Debye law for an ideal two-dimensional crystal especially
for 3He and 4He on graphite (Bretz et al. 1973; Hering et al. 1976). The
peaks in the specsc heat are identified with the melting transition. This
414 J.M. KOSTERLITZ AND D.J. THOULESS [CH. 5 , # 3

interpretation is consistent with the neutron diffraction peaks which gradually

broaden (Kjems et al. 1976).
The theory of the two-dimensional crystal near the melting temperature is
based on the harmonic approximation, ignoring quantum effects, so that the
Hamiltonian for an isotropic crystal is

wherepij is the stress and the strain uij is

with u the displacement of an atom from its equilibrium position. For an

isotropic crystal

Equation (3.57) is also true for two-dimensional hexagonal and triangular

lattices (Landau and Lifshitz 1959) the latter being relevant for helium on
graphite. As discussed in 0 2, the mean square deviation of an atom from its
equilibrium position is proportional to the logarithm of the area of the system,
so there is no positional long-range order (Mermin 1968). However, consider
the correlation function analogous to the superfluid or magnetic (V+ * V4}
correlation function [eq. (3.53)]

which is a measure of directional long-range order. Here R = na+mb is the

equilibrium position of an atom in the unstrained and r(R) the position in the
strained lattice. In the harmonic approximation, taking into account only
the long-wavelength phonon excitations, this quantity turns out to be equal
to u z at all temperatures. Hence the crystal has long-range directional but not
positional order (Mermin 1968).
A picture of such a system may be obtained by imagining an unstretched
rubber sheet with a lattice drawn on it. The long-wavelength excitations
correspond to stretching without cutting the sheet, so that locally the lattice
is perfect, but the displacements of the lattice points from their original
positions can be very large. It is difficult to imagine how correlations between
the crystal axes can be lost by such a process. If, however, we allow dis-
CH.5,O 31 TWO-DIMENSIONAL PHYSICS 415

Iocations and disclinations (Friedel 1944; Nabarro 1967) which correspond

to cutting the sheet, taking out or adding a piece and gluing the edges together
again in such a way as to locally restore the lattice structure, we can see that
directional correlationscan also be lost (see fig. 7).
The types of topological singularity,or defects,are slightlymore complicated
here than in magnets or superfluids. A given perfect lattice is invariant under
translation by R = na+rnb where u and b are the lattice vectors, but it is
also invariant under rotations through multiples of 0 = cos%b, the angle
between the lattice vectors, +n for a square and +a for a triangular lattice.
Thus, a crystal can have both translational singularities - dislocations of the
Burgers type-or rotational singularities-disclinations (Friedel 1964; Nabarro
1967). The latter are analogous to vortices in a superfluid and to disclinations
in nematic liquid crystals, while the former do not exist in these systems. In
smectic B liquid crystals, on the other hand, both can, in principle, exist.
In two dimensions, the description of such singularities becomes simple
since their position is specified by a point rather than a line as in three di-
mensions. If we take a closed contour around a disclination, a unit vector
rotates by a multiple of +n for a square lattice, and the displacementu changes
by an amount proportional to the radius of the coutour, while for a trans-
lational dislocation

gdu = b, (3.59)

where b is the Burger’s vector of the dislocation (Friedel 1964; Nabarro 1967).
Having identified the types of singularity which can exist, we must ask
about their energy. For a two-dimensional crystal an isolated disclination
has an energy proportional to the urea of the system and so is most unlikely
to occur since the energy will dominate the entropy for all temperatures. Note
that in superfluids and nematic liquid crystals the energy of an isolated dis-
clination (vortex) is proportional to the logarithm of the area. In what
follows, we shall therefore ignore disclinations.
Topological order in a two-dimensional crystal (Kosterlitz and Thouless
1972, 1973) can be defined in a very similar way to that of the magnetic or
superfluid case. Suppose the system has enough short-range order so that a
local crystal structure can be defined. Using the local order, we trace out a
path from site to site which, in the perfect crystal, would be closed. If there
are free dislocations present, the number of these within the contour will be
proportional to the area enclosed by the path, and so the total average
Burger’s vector will be proportional to the length L of the contour. If there
416 J.M. KOSTERLITZ AND D.J. THOULESS [CH.5,s 3

are only bound pairs of dislocations the average Burger’s vector will be pro-
portional to (JU)”~, where d is the mean separation. Note that even if we
allow long wavelength excitations, such a procedure as outlined above is
still possible because directional long-range order is not destroyed by these.

(b)
Fig. 7. (a) A disclination in a square lattice of 4 x fx. (b) A translational dislocation with
Burger’s vector b = (a, 0). The broken line is a typical contour round the dislocation which
would close in the perfect lattice.

If there are no free dislocations present, the system is rigid, while if free
dislocations are present an arbitrarily small shear stress will cause the dis-
locations to move to the surface and so a response characteristic of a viscous
liquid will ensue. Thus,the presence or absence of free dislocations determines
whether the system behaves like a solid or a liquid. In the same way as for
magnetic and superfluid systems, the rigidity modulus vanishes discontinuously
CH.5 , g 31 TWO-DIMENSIONALPHYSICS 417

at the melting temperature, but again this does not imply a first order tran-
sition.
Since the energy of an isolated dislocation of Burger’s vector b in a system
of area A is (Friedel 1964; Nabarro 1967)

E = b2p(A+p) log A / A , + O ( l ) , (3.60)

442p A) +
and the entropy S N log A / A o ,the melting temperature is then approximately

T, N b2p(A+p)/4n(2p +A). (3.61)

This can be written in terms of the transverse and longitudinal speeds of

sound (Elgin and Goodstein 1973,1974)

T, N (b2p/4n) C:(C,?- C:)/C,?, (3.62)

where p is the density of the layer. Since in helium layers C,?/Cf N 0.25
(Stewart 1974), we can rewrite eq. (3.62) as

T, N +
(b2p/4n) C:C,?/(C: C,?), (3.63)

which introduces errors of not more than 5%. As pointed out by Elgin and
Goodstein (1973, 1974) this is precisely the form derived by Feynman so that
either form will give the same value for T, to within 5%. Finally eq. (3.63)
can be expressed in terms of the measured value of the Debye temperature 0,

T, N 1.15 (mkB/32x2h2)a0e& (3.64)

where we have used b2 = 1.15ao where a. is the area of an elementary unit
for a triangular lattice. The predicted dependence T, aoOi is well obeyed,
N

but the values predicted by eq. (3.64) lie about 20% below the specific heat
peaks (Elgin and Goodstein 1973, 1974). This simple theory is expected to
overestimate the transition temperature since in the low temperature phase,
thermally activated dislocation pairs will tend to reduce the shear modulus
(Kosterlitz 1974). However, the underestimate may be caused by the use of
classical elasticity theory ignoring quantum effects of solid two-dimensional
helium.
To take into account interactions between the dislocations within the
harmonic approximation, we introduce a stress tensor ~ ( rwhich) is a scalar
418 J.M. KOSTEFUITZ AND D.J. THOULESS [CH. 5 , $ 3

in two dimensionsfrom which the stress can be calculated

One can then define a source function q(r) describing the distribution of
dislocations so that x(r) obeys the equation (Friedel 1964; Nabarro 1967)

V4x = Kq (3.65)

with

and

q(r) = c a
e i j - by) 6(r -dU)).
ar,

Here r@)and b(@are the positions and strengths of the ath dislocation. The
Hamiltonian eq. (3.56)becomes

(3.66)

If we now write x = x d + x o , where x d is the stress tensor due to the dis-

locations and xo due to the phonons, where V4x0 = 0, we can easily see that
the Hamiltonian becomes a sum of two terms

with Hd given by

(3.67)

subject to cSu= 0 and where p is the ‘chemical potential’ of a single dis-

location.
 CH.5 , # 31 TWO-DIMENSIONAL PHYSICS 419

We can see from eq. (3.67) why the scaling procedure of Kosterlitz (1974)
is more complicated than for the magnetic system. When two dislocations are
very close to each other, they can be regarded as a single dislocation of
strength 6, +b, . The square lattice is relatively simple (except that eq. (3.67) is
not correct because of the lowered symmetry) because IS, +b2 I can take on
onlv two values 0 or 2a, where a is a lattice spacing. In a triangular lattice, on
the other hand, we must also allow for the possibility 16, +S2 I = a. This does
not change the form of the scaling equations from those of eqs. (3.31) but the
analysis is more complicated.
The predictions are as in the magnetic system. There is a sharp transition at
a definite temperature which is of infinite order. The specific heat is smooth
at T, (a = -a)and as yet we cannot tell if the maximum occurs at T, or
some other temperature. The rigidity modulus as defined as the response to an
infinitesimal shear stress

(3.68)

vanishes discontinuouslylikethe superfluid density. Note that this is not incon-

sistent with a continuous transition.

3.7. EPITAXIAL
MONOLAYERS

The atoms of gas are preferentially adsorbed at the centres of the graphite
hexagons (Dash 1975). Owing to the size of the adsorbate atoms, not every
site can be occupied, but if every third site is occupied the adsorbate forms a
regular triangular lattice, and so should be an excellent experimental realisa-
tion of a lattice gas, in which an ordering field produces deviations from this
critical coverage. At the critical coverage (a 4 3 x 2/3 epitaxial structure) the
specific heat anomaly for 3He and 4He on graphite is very pronounced, and
in the range lo-' > I 1 -TIT, I > 5 x 10- fits well to a logarithmic CINk, N
Alog I 1 -TIT, I +B with values of A quite close to the theoretical value for
the two dimensional Ising model (Dash 1975).
However, the critical coverage for the theoretical Ising lattice gas cor-
responds to a critical coverage of 0.5, rather than 0.33 for the experimental
system. Alexander (1975) has suggested that the monolayer corresponds to a
three state Potts (1952) model since there are three possible equivalent
ordered states as shown in fig. 8. This model has a continuous transition
(Baxter 1973) in two dimensions which is consistent with the experimental
observations. For other gases on graphite, however, the transition appears
420 J.M. KOSTERLITZ AND D.J. THOULESS [CH. 5 , s 4

first order. In the case of Xe there is evidence of two phase coexistence, while
for N2there is still controversy (Dash 1975), although a recent paper (Butler
et al. 1975) finds the data consistent with a clussicul transition! Clearly much
work both experimental and theoretical remains to be done to clarify the
effects of the substrate on different gases.

Fig. 8. The three possible equivalent orderings of 4He atoms adsorbed on graphite at
critical coverage. The lattice sites are the centres of the graphite hexagons.

4. Metal-insulator transitions

4.1. THEPERCOLATIONMODEL

A simple model which can display either insulating or conducting properties

is a system which is made up randomly of insulating and conducting material.
This is the percolation model, which has been quite extensively studied as a
model of random magnetic systems, composed of magnetic and nonmag-
netic atoms. The model is usually formulated in terms of a lattice, and there
are two versions of the model, bond percolation and site percolation. In the
bond percolation model the lattice sites are connected by bonds which have
a probabilityp of being available (conducting) and a probability q = 1-p of
not being available. In the site problem the sites have a probabilityp of being
available, and the bonds between two neighbouring available sites are always
available. In fact the bond problem can be regarded as a special case of the
site problem. When p is below a certain critical value pc there are only finite
clusters of connected sites, but when p exceeds pc there will be an infinite
cluster of connected sites, as well as finite unconnected to the main cluster.
CH. 5,# 41 TWO-DIMENSIONAL PHYSICS 421

There have been reviews of percolation theory by Shante and Kirkpatrick

(1971), by Essam (1972), and by Kirkpatrick (1973).
The two-dimensional percolation problem has attracted quite a lot of
attention for various reasons. The one-dimensional problem is trivial, since
there are no infinite clusters in that case unless p is unity, so the two-dimen-
sional case is the simplest nontrivial case. There are some exact results
available which were derived by Sykes and Essam (1964) who exploited a
property of two-dimensionalspace which has no analogue in three dimensions.
The simplest form of their argument can be used to show that the critical
probabilityp, for site percolation on a triangular lattice is 3. This argument is
illustrated in fig. 9. If the black circles denote available sites and the open
circles unavailable sites, there is a finite cluster of available sites shown in the
figure which is surrounded by a perimeter of unavailable sites. If there are

. 0 0 0 0 0

O . . O O .
0 0 0 . 0
Fig. 9. Percolation model in a triangular lattice. The open circles denote unavailable sites
and the filled in circles available sites. There is a cluster of five available sites shown in this
diagram.

only finite clusters of available sites then the unavailable sites surrounding
them must form an infinite cluster, but it is not possible in a random arrange-
ment for there to be infinite clusters of both kinds (a non-random arrangement
could have infinite strands of both available and non-available sites inter-
leaved). A similar argument shows that pc for the bond problem on a square
lattice is also 3, so that an infinite square network falls to pieces once half the
bonds are broken. A more subtle version of the argument for the bond prob-
lem on a triangular lattice shows thatp, = 2 sin 10".
For most other problems the critical probability has to be estimated by
power series methods or Monte Carlo methods.
The knowledge of exact values ofp, for certain lattices allows power series
and Monte Carlo methods to be used to calculate certain critical exponents,
such as the one giving the dependence of the number of sites in the infinite
cluster on p-p, or the dependence of mean cluster size on pc-p, with con-
C
422 J.M. KOSTERLITZ AND D.J. THOULESS [CH. 5 , s 4

siderable accuracy, and various estimates have been made recently (Dunn et
al. 1975; Sykes and Glen 1976; Sykes et al. 1976; Gaunt and Sykes 1976;
Cox and Essam 1976), all in fairly good agreement.
The problem of the conductivityof a network in which resistors are removed
at random, which is a percolation problem, has received some attention in
recent years, because of its suggested relevance to a number of physical
situations. Ziman (1968) proposed it as a model of the behaviour of electrons
in a random medium, arguing that electrons of a certain energy would, if
they behaved classically, be able to move in regions whose potential was lower
than the electron energy, but would not be able to move where the potential
was higher. If the fluctuations of the potential about the mean potential are
symmetricalpercolation can occur in two dimensions once the energy is above
the mean value, as can be shown by the argument used to show that p E =
for the triangular site problem. Ambegaokar et al. (1971) have invoked
percolation theory in their derivation of Mott's (1969) variable range hopping
conductivity formula. In this problem the relevant critical probability is the
minimum density of points p , which can be joined together by bonds whose
length is less than ro to form an infinite cluster. Various estimates ofp, have
been made (Dalton et al. 1964; Ottavi and Gayda 1974), and a recent value
quoted is (4.4&0.2)/nr; (Fremlin 1976).
The conductivity of a two-dimensional percolation system has been
studied by physical simulation. Last and Thouless (1971) punched holes in
conducting paper, and Watson and Leath (1974) cut links in chicken-wire.
Kirkpatrick (1971) used a computer simulation to study the same problem.
It was found that for p well above p , the conductivity can be fitted by an
effective medium theory (Landauer 1952), but that as p approaches pc the
conductivity curve flattens out, so that it is proportional to (p-pc)', where
the exponent t is about 1.3. Stinchcombe and Watson (1976) have used real
space renormalisationgroup methods to calculate this exponent, and obtained
a slightly lower value. The value of this exponent is also of significance for
magnetic systems, since the spin-wave stiffness near the percolation limit
depends on it (Kirkpatrick 1973).
Various physical systems which might be expected to have two-dimensional
percolation properties have been studied. Abelks et al. (1975) have looked at
heterogeneous films of tungsten and AI,O, and measured the conductivity;
the results are not altogether in accord with the predictions of percolation
theory. Liang et al. (1976) have studied the conductivity of bismuth films
under conditions in which the films gave only partial coverage, and the
coverage at which metallic conduction occurs is in accord with percolation
CH.5 , g 41 TWO-DIMENSIONAL PHYSICS 423

theory. Arnold (1976) has interpreted the conductivity of inversion layers in

terms of percolation theory.

4.2. ANDERSON
LOCALISATION

Since electrons are not classical particles but obey the laws of quantum
mechanics, the percolation model is only directly relevant when the length
scale of potential fluctuations is much longer than the wavelength of an
electron. When the fluctuations have a short range the electrons can tunnel
from one region of favourable potential through an unfavourable region to
another favourable region, so one should not expect an abrupt change in the
nature of the system at the percolation limit. However, Anderson (1958) has
argued that in a system with a random potential electrons will be localised if
the disorder is sufficientlygreat.
These localised electrons form a continuous energy band, but the wave
functions fall off exponentially from some maximum value, which may be in
any region of the homogeneous system, and conductivity can only occur if
energy is supplied by the phonons to carry an electron from one localised state
to a neighbouring, which inevitably has a slightly different energy. At low
temperatures this gives rise to Mott's (1969) variable range hopping with the
characteristic exp -(T0/T)'l3 temperature dependence in two dimensions.
When the disorder is less strong there may be extended Bloch-like states in the
centre of the energy band, with a metallic conductivity, but in the tails of the
band, outside some mobility edge, the states will be localised. The theory of
localised electron states has been reviewed by Thouless (1974).
As in the percolation model the two-dimensional system has received a lot
of theoretical attention because it is the simplest non-trivial system. Mott and
Twose (1961) showed that electrons are all localised in one dimension however
small the disorder. Khor and Smith (1971) did numerical calculations for
samples of two-dimensional lattices and showed convincingly that the states
at the band edge were indeed exponentially localised. Further calculations
have been carried out by Edwards and Thouless (1972), Kikuchi (1974, 1976),
Licciardello and Thouless (1975b) and Yoshino and Okazaki (1976). These
studies have all shown a transition between localised and extended states as
expected, but have shown that Anderson's (1958) estimate of the degree of
disorder needed to localise electrons was far too high; electrons are much
easier to localise than his theory predicts.
The two-dimensional localisation problem became particularly interesting
when it was realised that electrons in an inversion layer could provide an
424 J.M. KOSTERLLTZ A N D D.J. THOULESS [CH. 5, # 4

example of this phenomenon (Pepper et al. 1974; Mott et al. 1975). Mott
(1970, 1974) has argued that the wavelength of an electron cannot be sub-
stantially less than the mean free path A, the distance in which the electron
loses phase coherence, and if the criterion kA > 1 is applied to the formula

u = ne2 A/mv (4.1)

for the conductivity in two dimensions, using n = k2/2n,the result

1 e2
d > --
2n A

is obtained. Licciardello and Thouless (1975a) have argued that this minimum
metallic conductivity has a universal value in two dimensions, and have
estimated its value as 0.12f0.03 e2/A. The argument is that localisation will
occur if the amount by which conditions at the boundary of an area of side L
can shift energy levels, which we call AE, is much,less than the spacing between
levels q, in this case states confined to the volume will be little perturbed by
neighbouring volumes, and so will be exponentially localised. If the electrons
are Bloch-like with a mean free path 1,AE is equal to A divided by the time it
takes an electron to diffuse to the boundary, so

AE = h D/L2, (4.3)

where D is the diffusion constant, provided L is much greater than A. The

condition for localisation is then

AE hD
- = -n(E)L2 < 1. (4.4)
rl L2

From the Einstein relation between the diffusion constant and the con-
ductivity this is equal to 2uA/e2, and so the condition for the existence of
extended states can be expressed in terms of the conductivity without reference
to the details of the microscopic structure of the solid. This relation is a
special feature of two-dimensional systems, and the observation of minimum
metallic conductivitiesof this order of magnitude is an important verification
of the theory (Pepper et al. 1974; Pepper 1977).
The experiments of Tsui and Allen (1974) and Hartstein and Fowler (1975)
show that not all the phenomena connected with the transition from local-
CH.5,B 41 TWO-DIMENSIONAL PHYSICS 425

ised to extended states can be understood in these terms alone. There is

nothing in this argument that forces the metallic conductivity to reach this
minimum value before the transition occurs. It has been suggested (Adkins
et al. 1976) that when there are inhomogeneities on a scale large compared
with the wavelength the metallic conductivity is higher at the transition,
because the inhomogeneity forces the conduction into restricted channels so
that the system behaves more like a one-dimensional system in which states
are always localised. Although some attention has been paid to the cross-over
from localisation under the influence of short-range fluctuations to the per-
colation regime (Toulouse 1975; Friedel 1976), there has not yet been a
satisfactorystudy of the problem.

4.3. DENSITY
WAVES

There are many mechanisms which may give rise to a metal-insulator trans-
ition in a solid, which are reviewed in the book by Mott (1974). The only
mechanisms which seem to have been explored in detail for the particular case
of two-dimensional systems are Anderson localisation, discussed in the pre-
vious section, and the formation of charge density waves or spin density waves.
Charge density waves in metallic layer compounds have been discussed in
the review by Wilson et al. (1975). The mechanisms producing charge density
waves and spin density waves are rather similar, but charge density waves are
favoured by the electron-phonon interaction, which acts as an effective
attractive interaction between electrons, while spin density waves, which keep
electrons of opposite spin apart, are favoured by the repulsive Coulomb
interaction between electrons (Chan and Heine 1973). In one-dimensional
systems these density waves occur however weak the interaction but in two or
three dimensions thay can only be made at the expense of increasingthe band
energy, and how much this increase is depends on the detailed shape of the
Fermi surface. The formation of such waves is particularly easy if there are
flat parallel regions of the Fermi surface, and the small dependence of the
energy on the component of momentum perpendicular to the planes makes
the layer compounds and other two-dimensional systems particularly suitable.
When density waves are set up they will generally occur as a pattern of
standing waves with two sets of nodal planes, and so their effect is quite com-
plicated. It is easier to consider the stability of the state without density waves
when subject to a perturbation of the sort that a density wave would produce.
If the state is unstable then a density wave will be set up. We therefore
426 J.M. KOSTERLITZ AND D.J. THOULESS [CH.5 , s 4

consider the effect of a perturbation of wavenumber on a Fermi gas and

calculate the susceptibilityto such a perturbation. This is a standard problem
in many-body theory, and for the case of a charge density wave driven by an
attractive interaction whose matrix element is a constant - V the condition
for stability is

wherefis the Fermi function, &k is the band energy and the factor 2 comes
from the sum over spin states. If there are flat parallel planes in the Fermi
surface, separated by wave number Q, then if k is at a distance x below the
Fermi surface and k + Q is a distance x above it, the value of & k + Q - & k is
h2Qx/m*. At low temperatures the integral over x in eq. (4.5) will then diverge
logarithmically, and so the instability must occur at some temperature. In the
trigonal(1T) phase of the layer compounds the Fermi surface is as shown in
fig. 10a, and a value of Q as shown in this figure will carry electrons in several
regions of the Fermi surface close to another region. When the instability sets
in a superlattice is formed, which need not be commensurate with the crystal
lattice and gaps open up on those parts of the original Fermi surface connected
by a reciprocal lattice vector of the new superlattice, so that the system
becomes insulating.
Rice and Scott (1975) have argued that for the hexagonal (2H) phases the
Fermi surface comes close to six saddle points, as shown in fig. lob. These
are points of high density of states, and therefore a value of Q that connects
pairs of saddle points can make the right side of eq, (4.5) large and produce
an instability. If a superlattice is formed in this way it will not reduce the
area of the Fermi surface significantly, but it will push the Fermi surface away
from these regions of high density of states and so reduce the scattering of
electrons. This is therefore an explanatioa for the enhanced conductivity of
the 2H phases when a superlattice is formed.
Kelly and Falicov (1976) have proposed that a superlattice is formed by
charge density waves in an inversion layer. This is used to explain various
anomalous results such as the fact that there only appears to be a two-fold
orbital degeneracy instead of the six-fold degeneracy expected on the (1 11)
surface of silicon.
A summary of various other aspects of many-body effects in inversion
layers and for electrons on helium surfaces has been given by Stern (1976) in
his summary of a conference devoted to these materials.
CH.5.8 41 TWO-DIMENSIONAL PHYSICS 427

Ia). b)
Fig.10. Schematic Fermi surfaces for layer compounds. (a) shows the Fermi surface for
the 1T phase, and (b) for the 2H phase. The wave number for a possible charge density
wave is shown in each case by Q.

4.4. THEWIGNER LATTICE

Wigner (1938) pointed out that the electron gas should at sufficiently low
temperatures condense to a solid-like lattice structure. It is likely that suitable
conditions for the formation of such a lattice could be attained either for
electrons on the surface of helium, or for electrons in an inversion layer and
so there has been a considerableinterest in the theory of the Wigner lattice.
Bonsall and Maradudin (1976) have shown that the lowest energy con-
figuration of the electrons in two dimensions is a close-packed triangular
lattice, and they have found the normal modes of vibration of the system,
which are a longitudinal plasma mode whose frequency is proportional to
q'/2 for small wavenumber q and a transverse sound wave with frequency
linear in q. Platzman and Fukuyama (1974) have studied the stability of the
system taking account of nonlinear effects in a self-consistent way and allow-
ing both for thermal and quantum zero-point motion. In this way they have
estimated the melting curve of the lattice in terms of the two dimensionless
parameters e2n1/2/(4mOkBT) and e2m/(4mOh2n1/2) where n is the density of
electrons.
Hockney and Brown (1975) have carried out a molecular dynamics calcu-
lation for a system of lo4 electrons confined to a square region with periodic
boundary conditions. They calculated both the specific heat and the structure
factor over a range of temperatures. The area of the square was 10-"m2, so
the density was 1014 electrons/m2. They found that at low temperatures a
triangular lattice was formed, and as the temperature was raised it seemed to
428 J.M. KOSTERLlTZ AND D.J. THOULESS

break into a polycrystalline state, and there was a fairly sharp phase transi-
tion to a disordered state at 3.1 K. This transition has a well-defined specific
heat singularity with a specific heat exponent equal to 0.08 below the transi-
tion and 0.14 above, so it is sharper than the two-dimensionalIsing transition.
These results raise a number of interesting questions. In the first place the
transition temperature is lower by a factor of 30 than the temperature calcu-
lated by Platzman and Fukuyama (1974) in the classical limit, so doubt must
be cast on all results obtained by similar arguments. The temperature is so
low that the disordered state just above the transition has only a small
fraction less correlation energy than the ground state. The existence of an
ordered state at low temperatures is somewhat odd since the Peierls (1934,
1935) argument would say that the transverse sound wave must destroy long-
range order for a sufficiently big system, but since we know a number of
other examples of systems with phase transitions to which the same argument
can be applied it is not very surprising. If the breaking up of a single crystal
into a polycrystalline form below the transition temperature is a real feature
of system, and not just an artifact due to the difficultyof fitting a triangular
lattice into a square area, it presents an interesting challenge to statistical
mechanics.
The question of how an electron lattice can be detected once it is formed is
a challenging one, and it would be helpful to have a firm theoretical pre-
diction before experiments are done. It can be argued that a lattice will be
pinned by the substrate and so the system will be an insulator, which might
be hard to distinguish from Anderson localisation or a Mott insulator. It
can also be argued that the system will not be readily pinned, since the poten-
tial energy of the whole lattice, not just of individual electrons, is in question,
and this varies by a relatively small amount (of order N'/2, where N is the
number of electrons) from point to point, unless the electron lattice is com-
mensurate with the substrate lattice. If this is right one might expect the con-
ductivity to be high, with the lattice moving as a whole.

Note added in proof

Since this article was written, there has been a great deal of activity in two-
dimensional physics, especially on the planar rotator model and its generali-
sations. Monte Carlo simulations have shown that vortex like codgurations
do develop (Suzuki et al. 1977; Kawabata and Binder 1977). JosC et al.
(1977) have made a study of the planar rotator model with symmetry
breaking fields by the Migdal (1975) renormalisation group technique. They
 TWO-DIMENSIONAL PHYSICS 429

also rederived the recursion relations (3.3 1) working on a lattice throughout

via duality relations. On the way they showed the equivalence of the discrete
Gaussian model of the roughening transition, which is important in theories
of crystal growth, to the Coulomb gas and planar rotator models (see also
Chui and Weeks 1976). They further generalised the method described in
$3.3 to cope with symmetry breaking fields by the introduction of two
different types of vortices. Kadanoff (1977, 1978) has taken this approach
further and has shown that a number of two-dimensional models such as the
%vertex and Ashkin-Teller models can be mapped on to a generalised
Coulomb gas problem with interacting electric and magnetic charges.
Nelson and Kosterlitz (1977) have shown that the quantity p,(T)/T, as
T + Tc-, reaches the coverage independent universal value of 2rn2kBlnn2=
3.52 x g.cm-’K-’ as predicted from the naive theory of single vortex
formation. This result is an inescapable prediction since, at T,, all other
effects which could be present in a superfluid film of 4He are irrelevant. An
experimental measurement of this quantity will provide a check on the theory.
Unfortunately experiments on 4He films (Bishop and Reppy 1977) are done
at finite frequency and the critical dynamics must be investigated. Some
progress has been made very recently with encouragingresults by Ambegaokar
et al. (1978), Huberman et al. (1978) and Chui and Weeks (1978).

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This Page Intentionally Left Blank
 CHAPTER 6

FIRST AND SECOND ORDER PHASE

TRANSITIONS OF MODERATELY SMALL
SUPERCONDUCTORS IN A MAGNETIC FIELD
BY

H.J. FINK
Department of Electrical Engineering,
University of California,
Davis, California 95616, USA

D.S. McLACHLAN
Department of Physics,
University of the Witwatersrand,
Johannesburg 2000, South Africa

B. ROTHBERG-BIBBY *
Department of Physics,
University of the Witwatersrand,
Johannesburg 2000, South Africa

*Present address: 9 Walnut Way, Maungaraki, Lower Hutt, New Zealand.

Progress in Low Temperature Physics, Volume VIIB

Edited by D.F.Brewer
Q North-Holland Publishing Company, 1978
Contents

1. Introduction 437
1.l.General considerations - Landau critical point 437
1.2. General considerations - thio superconductors 437
1.3. General considerations - bulklimit 439
1.4. Limitations of article 442
1.5. Objective 443
2. Theoretical results 443
2.1. Ginzburg-Landau theory 443
+
2.2. Phase transitions for Fa 1 446
2.3. Superheating for temperatures below the LCP 451
2.4. Supercooling for temperatures below the LCP 459
2.5. Thermodynamic critical field for temperatures below the LCP 462
2.6. Summary of various critical field approximations for other considerations 462
2.7. Penetration depth 463
2.8. Recent theoretical developments 473
3. Experimental techniques 474
3.1. Sample preparation 475
3.2. Measuring techniques 476
4. Second order phase transitions and the Landau critical point 479
4.1. Introduction 479
4.2. Behavior of the order parameter 480
4.3. First and second derivatives of the free energy 481
4.4. Critical field measurements in the second order region 485
4.5. Landau critical point 487
4.6. Thermodynamic critical field 489
5. First order transitions - superheating and supercooling 489
5.1. Introduction 489
5.2. Low K type I coated and uncoated superconductors 493
5.3. Intermediate K values and the metastable surface sheath 502
5.4. Low K type I1 superconductors and the observation of individual fluxoids 503
5.5. Measurement of 6(T,H) 506
5.6. Study of metastable phases of elements and alloys 507
5.7. Transition and nucleation times 508
5.8. Applications 508
5.9. Recent experimental developments 509
Appendix - derivation of equation (2.57) 511
List of symbols 512
References 513
1. Introduction

CONSIDERATIONS- LANDAU
1.1. GENERAL CRITICAL POINT

As the temperature is increased from absolute zero to the transition

temperature T, of a superconductor,* the penetration depth A(T) and the
coherence length t ( T )increase from a finite value at absolute zero to infinity
at T,. A moderately small superconductor is defined as one which has at
least one dimension perpendicular to the applied magnetic field which is
comparable to A(T) at a temperature T = TL which is defined below as the
Landau Critical Point (LCP) temperature. This definition excludes a thin
film in an applied magnetic field perpendicular to its surface. Depending upon
the geometry, the temperature TL is directly related to the smallest dimension
of the specimen, and the ratio of the critical field HL at which the LCP occurs
to the bulk critical field H,(TL) is a constant which depends only on the
geometry of the specimen. For temperatures below TL the superconductor
makes a first order magnetic phase transition to the normal state in a large
magnetic field and for T > TL it makes a second order phase transition. We
assume that the smallest specimen dimension is considerably larger than A(0)
such that TL is defined. This definition eliminates very small and very thin
superconductors. For these Bardeen (1962) also calculates a critical point
which, however, does not depend on the sample size but on the material
parameters N(0) and V(BCS). The latter has not yet been experimentally
found. The similarities between the Bardeen critical point and the LCP are
discussed in the appendix of Rothberg Bibby (1975). On the other hand, the
specimens under consideration should not be too large in comparison to
L(T), otherwise the temperature range between TLand T,will not be readily
accessible to experimentation. Typically, superconductors with at least one
spatial dimension in the micrometer range have a LCP temperature TL
around 50 millidegreesbelow T,.

CONSIDERATIONS - THIN SUPERCONDUCTORS

1.2. GENERAL
To illustrate the meaning of the LCP we consider fig. 1 which shows calcu-
* A list of symbols is printed after the appendix.
438 H.J.FINK ETAL. [CH. 6,8 1

lations (solid lines) of three critical fields by Feder and McLachlan (1969)
and Feder (1970) for a moderately thin film of thickness din a magnetic field
parallel to its surfaces. The experimental points and the curves for K = 0.13
(broken lines) are from Pellan et al. (1973). Very close to T, the value of A(T)
2 d and the phase transition from the superconducting to the normal state
and vice versa is of second order (Landau 1935). As the temperature is
lowered (d is fixed) A(T)decreases and when I(T) = rZ(TL)= d/2/5 the LCP
is reached. For values of I(T) < A(TL),that is for lower temperatures, there
exist 3 critical fields for a superconductor whose Ginzburg-Landau (1950)
K-value [K = I(T)/<(T)]is small compared to unity.

I"
'b
I

1 5 10 50 100
d/X(T)
Fig. 1. Superheating field H.,,, thermodynamic critical field HT and supercooling field
H,. for a film of thickness din a magnetic field parallel to its surfaces calculated from the GL
theory in the approximation K 4 1. Solid lines are from Feder and McLachlan (1969).
Experimental points of small indium squares, 1 .O pm thick, and curves for K = 0.13 (broken
lines) are from Pellan et al. (1973).

The theoretical superheating field Hshis defined as the field up to which a

metastable solution of a homogeneous superconducting state exists when
calculated from the Ginzburg-Landau (GL) equations for a given geometry.
At this field the Gibbs free energy of the superconducting state G, is larger
than that of the normal state G, and the superconductor goes into the normal
state by a first order magnetic phase transition as the magnetic field is in-
creased.
CH.6,g 11 SMALL SUPERCONDUCI'ORS IN MAGNETIC FIELD 439

The thermodynamic critical field HT is defined as the field at which the

Gibbs free energy of the homogeneous superconducting state G, is equal to
that of the normal state G,. If the homogeneous superconducting state is a
lowest free energy solution up to HT, then the transition is usually a reversible
first order phase transition. For moderately small specimens the homogeneous
superconducting state is stable for H c HT and metastable for H > HT.
The critical field HScis the supercooling field and can be observed when the
applied magnetic field Ho is decreased from above HT while the supercon-
ductor is in the normal state. If at Ho = HT the specimen does not make a
transition to the homogeneous superconducting state and remains in the
normal state as Ho is decreased below HT, then G, > G, and the normal state
is metastable. This state may persist until superconductivity nucleates by a
second order phase transition. The smallest value of this field is H,, at which
an infinitesimally small amount of superconductivity must nucleate. Once a
nucleation center is established, superconductivity usually spreads quickly
throughout the specimen which then makes an apparent first order transition
to the Meissner state.
We shall limit this article principally to type I superconductors. For these,
as can be seen from fig. 1, H,,/Hc decreases as d/A(T)is decreased, reaches a
minimum at d N 4.5A(T), then increases for smaller values of d/A(T) and
merges at the LCP, located at d = &A(T), with the supercooling curve.
Similar results were obtained by Esfandiari and Fink (1975) for a cylinder of
radius a in an axial magnetic field where it was found that H,,/H, has a
minimum at a N 4.2A(T) for all K values smaller than approximately 0.5. By
contrast HT and H,, increase smoothly in fig. 1 when d/A(T>is decreased for
all values of d/A(T).

CONSIDERATIONS - BULK LIMIT

1.3. GENERAL
As the temperature is lowered further, 1(T) may become much smaller than
d and the specimen tends to become a bulk superconductor. Whether this
transition to the bulk configurationis accomplished for a given specimen with
thickness d or not depends on the values of A(0) and t(0). If we limit our
considerations to specimens with K ;5 1 the value of A(T) is the controlling
characteristic length. When ((7") = A(T)/Kis of the order of the smallest
sample dimension additional size effects occur.
Figure 2 shows a number of critical fields for a bulk specimen with zero
demagnetizing field. The curve for Hsh is from Fink and Presson (1969).
For K < 1.1 the value of Hshis defined as above and for IC > 1.1 two curves
440 H.J. FZNK ETAL. [CH. 6,s 1

are shown both of which are theoretical results. The upper is the maximum
field the GL eqs. permit, which, however, is unstable and is indicated by the
broken line. The upper limit of metastability for K > 1.1 is indicated by the
solid curve Hsb. Neither curve has been confirmed yet by experiments. For
K + co the value of Hsh + O.745Hc (Kramer 1968), where H, is the bulk
thermodynamic field. Hshis most likely the upper experimental limit.
1.6

1.5

1.4

1.3

13
r"
\
0
r
1.1

1.0

0.9

0.8

0.7
0.3 0.5 1.0 3.0 5.0 10.0
a
Fig. 2. Critical magnetic fields of a bulk superconductor without demagnetizing field.
is the superheating field. The lower curve for K > 1.1 is the upper theoretical limit of
metastability for HSh and the broken line is the maximum theoretical field which is physically
unstable. For K > 1.1 neither curve has been confirmed yet by experiments. Hc3 and Hc2
are the surface and bulk nucleation fields respectively. Hc3 is also equal to the supercooling
field H, for a free surface for small K values (seetext) and HC2 = H., if the surface sheath
is completely eliminated. He,is the lower critical field for flux entry into type I1 super-
conductors (K > 1/ 4 2 ) . Hmhis the lower limit of the metastable surface sheath.

Hshwas calculated first by Ginzburg (1958) for a bulk superconductor for

K $ 1. He finds that
CH. 6,s 11 SMALL SUPERCONDUCTORS IN MAGNETIC FIELD 441

The constant 0.89 was obtained by numerical integration at K = 0.02. The

Orsay Group (1966) and Caroli (1967) found by an analytical approximation
forlc 4 1

Poulsen and Fink (1974) numerically calculated Ha,,for the semi-infinite

superconducting half space for K values from above unity to K = 0.001.
Their results are discussed below.
+
In the extreme non-local limit, that is, when ic2 4 (1 -TITc) 1, the non-
local bulk superheatingfield is (Smith et al. 1970)

Hg,/Hc= 1. 3 6 / ~ ' / ~'(1~ ~ ' '.

-/T/TC)'/' (1-3)

The value of x is defined by eq. (2.4).

The surface nucleation field of a bulk superconductor

Hc3 = 2.397uHC (1.4)

is usually the same as the supercooling field provided K < 0.417 and the
surface of the specimen is not in contact with a metal in the normal state.
An exception to that rule is a metastable surface sheath which may surround
a bulk specimen. The latter may exist for a small range of magnetic fieldsjust
below Hc3for K values between 0.407 and 0.595 before a first order tran-
sition to the fully superconductingstate takes place (Feder 1967; Park 1967;
McEvoy et al. 1967; Smith and Cardona 1967a,b; Christiansen and Smith
1968; McEvoy et al. 1969).
If the surface of the superconductor is plated with a normal metal the
surface sheath may be partially or totally destroyed if the metal is ferro- or
antiferromagnetic (e.g. Barnes and Fink 1966). In the extreme limit, that is,
when the sheath is completely eliminated by the proximity effect, the super-
cooling field is for K < 1/42 equal to the bulk nucleation field

Hc2= d%Hc. (1.5)

There is no supercooling for type I1 superconductors.

At Hc3and Hc2the magnetic phase transition is of second order. If the
proximity effect is not effective in completely eliminatingthe sheath, or if the
normal metal makes poor contact with the superconductor, the supercooling
field for a bulk specimen may be anywhere between Hc3and Hcz.
442 H.J. FINK ETAL. [CH.6,s 1

Since the superheated Meissner state and the supercooled normal state are
metastable, transitions to the normal and superconducting states may occur
in an experiment before H , is equal to the theoretical values Hshor H,,
respectively. The full range of superheating and supercooling is usually
observed only in small spheres near T, where the coherence length or the size
of the nucleation centers become comparable to the size of surface defects.
H,, is the lower bulk critical field at which magnetic flux may enter the
Meissner state in an increasing magnetic field. It is defined by a relation
which equates the Gibbs free energy of the fully superconducting state in a
magnetic field with no fluxoid present to that with one fluxoid present. In
fig. 2 the values of H,, are from Harden and Arp (1963). Also solutions for
K < 0.707 are shown by the broken line. At H,, the magnetic phase tran-
sition is not of second or higher order.
Delayed flux entry into type I1 superconductors (Bean and Livingston
1964; Joseph and Tomasch 1964; DeBlois and DeSorbo 1964) when the
applied field H,, is increased beyond H,, is of the same physical origin as
superheating. The shielding currents at the surface of the specimen constitute
an effective barrier to the magnetic field pressure acting upon the specimen
from outside.

1.4. LIMITATIONS
OF ARTICLE

In practice all type I1 superconductorstrap flux and therefore have irreversible

magnetization curves. Hysteresis due to flux trapping by pinning will not be
discussed here. Furthermore, we shall not discuss hollow superconducting
cylinders whose diameters would classify them as moderately small; current
carrying characteristics of moderately small specimens, such as thin wires,
whiskers and microbridges; films in a magnetic field perpendicular to their
surfaces and the Josephson effect in moderately small specimens. Boundary
Effects and Small Specimens are discussed in a review by Burger and Saint-
James (1969).
In this article we shall base our discussion primarily upon the Ginzburg-
Landau theory (1950) which is relatively simple, conceptually, yet rich in its
phenomenological insight and powerful in obtaining critical magnetic fields,
although not always in a simple manner. This theory is based upon the
electrodynamics of superconductors by London and London (1935) which, in
turn, is based on the two-fluid model by Gorter and Casimir (1934a, b).
Gor’kov (1959a, b) showed that the GL theory can be derived in the ap-
propriate limits from the microscopic theory of Bardeen et al. (1957), thus
CH. 6,g 21 SMALL SUPERCONDUCTORS IN MAGNETIC FIELD 443

providing the basic justification for the GL theory. For a review of the
GL theory and a discussion of its limitations, see Werthamer (1969). The GL
theory provides a convenient foundation for understanding the basic phenom-
ena of size effects and magnetic phase transitions of superconductors and is
used throughout this article.

1.5. OBJECTIVE
The calculation and experimental verification of critical field diagrams
such as figs. 1 and 2, and the accurate measurement of K values for the
purpose of characterizingsuperconductorsis one of the primary objectives of
superheating and supercooling studies. Superheating and supercooling
measurements are the most reliable way of determining K values for type I
superconductors.

2. Theoretical results

2.1. GINZBURG-LANDAU
THEORY

The central part of the GL theory is the complex order parameter

W )= W) exp (i@(r)), (2.1)

which is analogous to a macroscopic wave function that describes the
center-of-mass motion of the electron pairs (or superconducting electrons)
I 1’
which are the essence of superconductivity. Y is proportional to the local
density of superelectrons which have an effective charge e* and effective mass
m* which is twice that of the free electron. The phase @ of the order parameter
describes the long range phase-coherence of the superconductingcondensate.
The total Gibbs free energy difference between the superconducting and
normal states consists of 3 terms: a negative contribution which arises from
the pairing energy of the superconducting ground state, a positive contri-
bution from the magnetic pressure difference between the local magnetic
field H(v) and the applied field Ha, and a positive contribution from the
kinetic energy of the superconducting electrons. It is in Gaussian units
(Ginzburg and Landau 1950)
444 H.J. FINK ETAL. [CH. 6, J 2

In eq. (2.2) the value of H,(T) is the bulk thermodynamic critical magnetic
field and the applied field Ha is that field which would be present if the
superconductor were removed. The integral extends not just over the volume
of the superconductor but over all space. If the demagnetization coefficient
is zero then the contribution of the volume integrals outside the supercon-
ducting body is zero; otherwise it is not, due to the magnetic pressure term.
I I’ 1 I’
Y, is the value of Y in zero magnetic field. Near T, it is

where n is the total number of conduction electrons per unit volume, T is

the ambient temperature, T, is the transition temperature of the supercon-
ductor and x = x(I) is a function of mean free path 1 (Gor’kov 1959b). It is
approximately

where 5(3) = 1.202, vF is the Fermi velocity and k is Boltzmann’s constant.

A large number of investigators have calculated critical fields and have
used various notations. In the interest of internal self-consistency,we shall use
the following notation and approach. One usually assumes that the relative
permeability of the metal is unity, hence V x A(r) = H(r) in c.g.s. Gaussian
units. It is convenient to cast eq. (2.2) into normalized units defined by

Q(r) = t( V@+$ A). (2.1 1)

Likewise, all distances are measured in units of the GL low field penetration
CH. 6,B 21 SMALL SUPERCONDUCTORS IN MAGNETIC FIELD 445

depth A = A(T) such that the normalized volume u E V/A3.Then eq. (2.2)
becomes

-F2+$F4+(VxQ-Ho)2+ (2.12)

F is the modulus of the normalized order parameter and Q is the normalized

superfluidvelocity.
If F and Q are equilibrium values then the first variation of g, namely

k = g(F+ JF, Q + JQ) -g(E Q), (2.13)

defines a minimum of g(F,Q) if 8g = 0 provided the second variation J2g > 0

(positive definite). If 8F and 8Q are arbitrary but small deviations from the
equilibrium values it follows from 8g = 0 that
V2F = x2(F2+ Q 2- 1)F, (2.14)
V X V X Q =- Q F 2 , (2.15)
VlsF = 0. (2.16)

In eq. (2.15) we have put V x Ho = 0, and eq. (2.16) means that the gradient
of Fis zero perpendicular to the free surface of the superconductor.
Let us consider the case of an infinitely long cylinder in an axial magnetic
field applied parallel to the z-direction. This case simulates experimental
results by Rothberg Bibby et al. (1975) on long crystal whiskers of tin and is
discussed in detail, as an example, in the subsequent theoretical sections.
To obtain exact solutions for the critical fields one expresses eqs. (2.14)
and (2.15) in cylindrical coordinates

(2.17)

(2.18)

where by symmetry F = F(r) and Q,(r) is the #-directed superfluid velocity.

Since the z-directed field is

(2.19)
446 H.J. FINK ETAL. [CH.6,g 2

one has to solve these equations with the boundary conditions dF/dr = 0
at r = a (radius of cylinder) and r = 0; Q = 0 at r = 0, and H, = H , at
r = a.
However, if a is of order unity (in conventional units of order A) and K Q 1
such that ( ( T )is much larger than the radius of the cylinder, one would expect
that F(r) is approximately independent of the spatial coordinates. We
therefore proceed similarly to Ginzburg (1958) by solving first eq. (2.18) with
F = F, = constant and substituting the result

(2.20)

into eq. (2.12) with FF = 0. After integration of eq. (2.12) one obtains for
the normalized Gibbs free energy differenceper unit volume

(2.21)

where I,, Zland I, are modified Bessel functions of the second kind.

2.2. PHASE TRANSITIONSFOR F

: 41
We investigate the magnetic phase transitions for a thin superconductor for
which F i may become very much smaller than unity in eq. (2.21). We
follow essentially, with some small modifications, the approach taken by
Rothberg Bibby et al. (1975). We assume that F,a Q 1 is satisfied so that one
can expand the last term in eq. (2.21) in a series. With the first 3 terms of the
series one gets

= AF:-+~BF:++cF:, (2.22)
0

where
A = H;a2/8 - 1, (2.23)
B = H,2a4/24- 1, (2.24)
C = 1 1 H;a6/1024. (2.25)

Depending on the values of A , B and C, that is, on the values of Ho and Q,

CH.6,s 21 SMALL SUPERCONDUCTORS IN MAGNETIC mELD 447

the function g/v has the limiting behavior shown schematically in fig, 3 for
F: 4 1. We define the following critical fields (the prime is the derivative
with respect to F,):
(a) thermodynamic size dependent critical field HT :
g = 0; g' = 0; g" > 0; Fi > 0.
(b) superheating field (largest possible) Hsh:
g > 0; g' = 0; g" = 0; g"' > 0; Fi >0

+
0

Fig. 3. Schematic representation of eq. (2.22) for limiting values of the applied field H o .

(c) supercoolingfield (smallest possible) Ha, :

g = 0; g' = 0; g" < 0 for F i = 0;
simultaneously a stable superconducting state should be possible into which
the metastable normal state can switch with the following properties:
g < 0; g' = 0; g" > 0; F,' > 0.
(d) If in (c) the latter state with F," > 0 does not exist, which is the case for
very thin specimens, then the transition is of second order with:
g = 0; g' = 0; g" > 0; Fi + 0.
448 H.J. FINK ET AL. [CH.6,5 2

Since
g p = A - BF: + CF;, (2.26)
g"/V = -B+2CF:, (2.27)

it follows from (d) and (c) that

A = 0 and B > 0 for supercooling, and

A = 0 and B < 0 for a second order phase transition.

The conditions A = 0 and B = 0 define the Landau critical point which (in
GL normalization) for a cylinder in an axial magnetic field is

H t = 813 (2.28)
a; = 3. (2.29)

In the supercooling and second order phase transition regions, critical field,
sample size and temperature are related by (A = 0)

Hi = 8/u2 (GL normalized units), (2.30)

where H , = H,,for a > 4 3 and H , = Hzp for a 5 43. The division

between the second order phase transition field and the supercooling field is
somewhat artificial, since superconductivitynucleates by a second order phase
transition on the surface of the specimen at the supercooling field. Once
nucleated, however, it switches to a superconducting state with F,' > 0 at the
supercooling field, whereas the superconductor does not have this opportunity
for HZp,that is, for a 4 4 3 .
For the thermodynamiccritical field the following solution is valid

- - 5>0
= or Bi = 16ATCT/3, (2.31)

and for the superheating field

Thus, eqs. (2.31) and (2.32) are of the same form except for a numerical
coefficient N(N,h = 4 and NT = 16/3).
CH. 6,g 21 SMALL SUPERCONDUCTORS IN MAGNETIC FIELD 449

When eqs. (2.28) and (2.29) are cast into conventional units, the LCP of a
cylinder of radius a in an axial field is defined by the following magnetic field
HLand temperature TL

H , = diZHc(0)A’(O)/a2, (2.33)
TL/Tc= t , = 1 -3A2(0)/4a2, (2.34)

where we have used the followingapproximations near T,

H, = H,(o)( 1 -t 2, N ~H,(o)(1 - i), (2.35)

A = A(O)/(l -t4)”2 N A(0)/2(1 --t)”2. (2.36)

With the definitions

(2.37)
(2.38)

where H,(t) and HL are in conventional units, eqs. (2.30) to (2.32) are normal-
ized with respect to the LCP and reduce to:

h& = At for 0 5 A t 5 1, (2.39)

htc = A t for A t > 1, (2.40)

N(hi - At)99hi/ 128 = (hi - 1)2 for A t > 1. (2.41)

When N = NT = 16/3 the value of 11, is identified with hT and when N = Nsh
= 4 the value of h, = h s h . Figure 4 shows a plot of eqs. (2.39H2.41) near
the LCP.
For an approximation to higher order in F, than given by eq. (2.22), one
finds that near the LCP the order parameter of a cylinder in an axial field for
a 2 2/3 is approximately

F,Z = ~ ( 1 -3/a2) (2.42)

with
a2 = 3At. (2.43)

y = yT = 32/33 forthe thermodynamic field and y = 7.h = 64/99 for the

450 H.J.FINK ET AL. [CH. 6.8 2

superheating field. From eq. (2.42) it is obvious that the range of appli-
I I
cability of eq. (2.41) for h, and hsh is A t - 1 4 1. Thus, it is necessary to
obtain an exact solution of eq. (2.21) when the latter restriction is not
satisfied.
Exact solutions of eq. (2.21) near the LCP are shown in fig. 5 by the solid
lines and should be compared to the results of fig. 4. The experimental points
are those of Rothberg Bibby et al. (1975) replotted for the [Ool] tin crystal

2 1 0

At
Fig. 4. Various critical fields near the Landau Critical Point (LCP) calculated from eqs.
(2.39H2.41). ho and A I are defined by eqs. (2.37) and (2.38) respectively. Magnetic
fields and temperature are normalized by the LCP.

whisker No. 21 at zero strain with HL = 10.18 G and Tc-TL 3 0.027 K.

These values are consistent with Hc(0) = 305 G, A(0) = 5.1 x 10-%m and
radius a = 5.2 x 10-%m. The different symbols of the points signify experi-
ments (discussed in detail in 34) on different days.
The agreement between the exact calculations and the experiments is then
a confirmation of the validity of the exact GL theory near T, for type I
superconductors at least for GL K values on the order of 0.1.
CH. 6,#21 SMALL SUPERCONDUCTORS IN MAGNETIC mELD 451

A comparison with the exact solutions shows that the value of Fo given by
eq. (2.42) is accurate to about 0.5% at the thermodynamic field for 4 3 5 a
6 10 and at the superheatingfield for 4 3 5 a I 3.

At
Fig. 5. Solid lines are exact critical fields of a cylinder in an axial magnetic field near the
Landau Critical Point (LCP) calculated numerically from eq. (2.21). Magnetic fields and
temperature are normalized by the LCP. ho and At are defined by eqs. (2.37) and (2.38)
respectively. The experimental points of a tin whisker are from Rothberg Bibby et al.
(1975). HL = 10.18 G, T,-TL = 0.027 K and T , = 3.723 K. Circles represent the differ-
ences between the fields at two observed transitions, one interpreted as the thermodynamic
equilibrium field and the other as the supercooling field. Squares represent the difference
between the only observed transition field, interpreted as the thermodynamic equilibrium
field, and the smooth interpolation between the supercoolingfield in the first-order region
and the unique transition field in the second-order region. The open and closed shapes
represent results obtained on different days. For further details see text.

2.3. SUPERHEATING FOR TEMPERATURES BELOW THE LCP

2.3.1, Cylinder in an axial magneticfield

In the limit that the radius a of a cylinder is very much smaller than the
coherence length <(T)one may neglect the term (VF/x)' in eq. (2.12), and then
452 H.J. FINK ET AL. [CH. 6 , $ 2

one obtains eq. (2.21) which was solved numerically by Esfandiari and Fink
(1975). This equation was minimized with respect to F,(dg/dF, = 0) and
the maximum magnetic field was obtained when the minimum of g became
an inflectionpoint as shown schematically in fig. 3 (d2g/dFi = 0). The super-
heating field Hsh,the corresponding order parameter F,, and the norma-
lized Gibbs free energy differenceper unit volume g/u are shown in fig. 6.
These results are valid when ax/A(T) < 1 (in conventional units). When
I2/Z0in eq. (2.21) is expanded for Foa 9 1 one obtains from g' = 0 and
g" = 0 an analytic approximation for Ha,,for large values of u/A which is eq.
(2.61) in table 1 .
0.8

0.6

0.2

0
1 2 3 5 7 10 20

ah
Fig. 6. Exact solutions of eq. (2.21) at the superheating field If.,,. Also shown are the
corresponding values for Fo . These results are valid for a 9 (.

If the above restriction u Q t(T)is not satisfied, then eqs. (2.17) and (2.18)
must be solved with the appropriate boundary conditions. Numerical results
for IC 5 1 are shown in fig. 7 (Esfandiari and Fink 1975). has a minimum
value of about 1.58HJT) when a N 4.2A(T) for all values of K < 0.5. This
behavior is similar to that of a thin film shown in fig. 1. The superheating
CH. 6,821 SMALL SUPERCONDUCTORS IN MAGNETIC mELD 453

field of a type I bulk specimen is reached when aK/A ;L 4.5. When

K 4 1 rather large values of a/A are required before one is allowed to make a
meaningful comparison between experimental values of Hahand theoretical
values obtained from the semi-infinite half space such as eqs. (1.1) or (1.2).
The minimum of H,,JH, as a function of a/A has its origin in the LCP at
which a first order magnetic phase transition merges into a secondorder phase
transition.

-0.1
1 2 3 5 10 20
Q Ih

Fig. 7. Superheating field as a function of cylinder radius a for various K values

calculated from eqs. (2.17)and(2.18).The applied field is parallel to the axis of the cylinder
From Esfandiari and Fink (1975).

2.3.2. Cylinder in transversefield

Figure 8 shows results similar to fig. 7 except that the magnetic field is applied
transverse to the cylinder axis (Esfandiari 1976). F and Q are both functions
of r and $ and their solutions are curved surfaces. For very large values of
a/A, that is, in the bulk limit, the values of Hshl are one-half of HshII
due to the
demagnetizingfield of a long cylinder.

2.3.3. Films and spheres

The only published superheating fields for moderately thin films are those
shown in fig. 1. No superheating fields have been published for arbitrary
values of K for films and spheres of arbitrary thicknessesand radii respectively.
D
454 H.J. FINK ET AL. [CH.6,4 2

2.3.4. Bulk superconductors

For sufficiently large specimens the superheating field of the semi-infinite
half-space is the upper magnetic field limit of a long cylinder in an axial field
for u/A > 1 and of a very thick film in a parallel field. Approximations are
given by eqs. (1.1) and (1.2). An exact solution for the semi-infinite half-space
is obtained by assuming that the surface is at x = 0, that the space for
x > 0 is filled with the superconductor and that the magnetic field is parallel

3.0

2.5

2.0

9
\

=f 1.5

1.o

0.5

0
1 2 3 5 7 1 0 20
a/A

Fig. 8. Superheating field H.,,as function of cylinder radius a for various K values for
cylinders in transverse. fields. From Esfandiari (1976).

to the positive z-direction. Equations (2.14) and (2.15) can be integrated

once in closed form in Cartesian coordinates. One useful result of the inte-
gration is

Since H(x) = dQ/dx and the magnetic field dependent penetration depth
S (normalized by the low field penetration depth A) is
CH.6, # 21 SMALL SUPERCONDUCTORSIN MAGNETIC FIELD 455

(2.45)

one obtains from eq. (2.44) at the free surface of a superconductor a relation
between H(0) = Ho (applied magnetic field), F(0) and 6 which is

(2.46)

Fig. 9. Order parameter F(0) at the surface of the metal is shown for the Meissner state
of semi-infinite superconducting half-space as a function of Ho/H,where Ho is the applied
field. The lower branch for Ho > H, is unstable and so is part of the upper branch near the
peak for K > 1.10. From Fink and Presson (1969).

It is known from solutions for the semi-infinitehalf-space (Fink and Presson

1969) that

(2.47)

at the maximum field which is equal to the superheating field for K < 1.1.
This is shown in fig. 9. When a variational calculation on the free energy g is
performed in the manner of the stability analysis by Fink and Presson (1969)
at the maximum field (k, = 0) at which eq. (2.47) applies, one finds that the
second variation 6'g is always zero. From this, one is not able to extract
456 H.J. FINK ET AL. [CH. 6,O 2

information concerning the field dependent penetration depth 6. However,

from the third variation Z3g = 0 one finds the following relation at the maxi-
mum field (Fink 1973)

[1 -FZ(O)]2
6'H; = (2.48)
1 - ZFZ(0)

Therefore, the surprising result emerges from eqs. (2.46) and (2.48) that at the
maximum field, regardless of the value of IC (conventionalunits)

611 = d2. (2.49)

2.0 , I I I

1.9 -
1.8-
1.7-
1.6-
------------------- ...
5.0 3.0
1.4- K =m
1.5
-
.
4

rg
1.0

1.3-

1.2-

HO'H,
Fig. 10. The dependence of 6/1(6 = maguetic field dependent penetration depth; 1 = low
field GL penetration depth) on the applied field H,,for various values of the Ginzburg-
Landau parameter K. From Fink and Kessinger (1967).

One can also show that the fourth variation of the Gibbs free energy b4g > 0
(positive definite). Equation (2.49) corroborates previous results by Fink and
Kessinger (1967) shown in fig. 10 and recent experimental results by Parr
(1975, 1976a). Equation (2.49) is valid for all K-values at the maximum
(mathematical) field which for K < 1.I is the superheating field. For K > I . I
CH.6 , I 21 SMALL SUPERCONDUCTORS IN MAGNETIC FIELD 457

10
-.
\,
- \
I

-.---Eq-
I I

(1.1)
I " 1 ' 1 I I I I I

-
-
- \

5-
-
I
"
>X"
3-
Eq. (l.Z)/

1 I 1 I I , I l l 1 1 I 1 1 1 1 1
0.01 0.03 0.05 0.1 0.3 0.5 1.0
a
Fig. 11. A comparison of the exact solution of the superheating field of the semi-infinite
superconducting half-space by Poulsen and Fink (1974) with approximationseqs. (1.1) and
(1.2).

For IC -+ 0 the value of d6/dF(O) + -2 and for K + a0 it approaches zero

at the maximum field. Equation (2.49a) is exact but differs considerably from
that used by Smithet al. (1970) which is d6/dF(O) = -F-'(O).
With eq. (2.49) and the auxiliary eq. (2.48), used as a consistency check, the
Ginzburg-Landau eqs. (2.14H2.16) were solved for K 4 1 by Poulsen and
Fink (1974) at the superheatingfield with the boundary condition (normalized
units)
-Q(O) = d T H 0 = dT(dQ/dx),=o. (2.50)
The results are summarized in figs. 11-13. The values of H,JHc for various
K--valuesare :

Ic 3 ~ 1 0 - lo-'
~ 3x10-' lo-' 3x10-' 1
Hsh/Hc 26.71 15.47 8.496 4.952 2.828 1.809 1.274
458 H.J. FINK ET AL. [CH.6, SI 2

X
Fig. 12. Solutions of the modulus of the order parameter F(x) and the superfluid velocity
Q(x) at the superheating field for various K values between 1 .O and 0.03. The coordinate x
is in units of the coherence length {(T)and Q(0)= H,,,/H,,

70.78

0.76

Fig. 13. Same as figure 12 except for K values between 0.03 and 0.001.
CH.6,f 21 SMALL SUPERCONDUCTORS IN MAGNETIC FIELD 459

An empirical fit through these points to better than 0.5% accuracy for
0 < K ;5 1is

H,,/H, = (1 + 0 . 6 5 8 ~ - 0 . 2 3 7 ~+’ O . ~ ” ~ C ’ ) / ~ ~ ’ ~ I C ’ ’ ~ . (2.51)

The normalized superfluid velocity at the surface of the superconductor is

directly related to the (maximum) superheating field by Q(0)= -Hsh/Hc.
Q(0)was found from the solutions shown in figs. 12 and 13. It required finding
the functions Q(x) and F(x) simultaneously, which satisfied, in addition to’
(2.50), the boundary conditions dQ/dx = 0 at x = ao, M/dx = 0 at x = 0 and
x = co,and F = 1 at x = 00. Only for K N 1.0 are the ranges of variation of
F(x) and Q(x) approximately equal, about 5 to 10 e(T). For K < 1 the function
Q(x), which is not an exponential function, varies very rapidly near x N 0.
However, Q(0) also increases very rapidly for decreasing K values and the
solutions had to be computed over distances of or larger to satisfy all
the boundary conditions. The exact solution of fig. 11 is also shown in fig. 2.

2.4. SUPERCOOLING
FOR TEMPERATURES BELOW TKE LCP

2.4.1. Cylinder in a magnetic$eldparallel to its axis

Near the LCP the maximum supercooling field of a cylinder in an axial field
is in conventionalunits

H,,/H, = 4L/a. (2.30)

Equation (2.30)is correct as long as r(T) $ a. When the radius of the cylinder
is larger than both A and g, eq. (2.30)does not apply.
For a bulk specimen the supercooling field is given for K < 0.417 by

H,, = H,, = 2.397~H,. (2.52)

For K > 0.417 supercooling does not take place since the second order phase
transition field Hc3 > H,. This is strictly correct only if one neglects the
possibility of a metastable surface sheath for IC values between 0.407 and
0.595, as discussed in $1.3.
For moderately small superconductors, that is, in the region between where
eq. (2.30)is valid and the bulk case, the supercoolingfield is the size-dependent
surface nucleation field. The nucleation field Hc3(a,n)= HIIof a cylinder in an
460 H.J. FINK ET AL. [CH.6,#2

axial magnetic field is implicitly a function of the number of fluxoids n en-

closed in the cylinder at HI,.Calculations by Saint-James (1965)are shown
in fig. 14 where the bulk nucleation field Ifc2 = d%HC = 40/2nt2 is
plotted as a function of the size-dependent surface nucleation field HII.Hr is a
reference field defined by Hr = 40/2na2, where +o = hc/2e is the flux
quantum. For n = 0 the solid curve in fig. 14 corresponds to eq. (2.30) which
is valid in the range
b
0 c a/( < 1.33 (2.53)

and is described by the equation (HI,= Hsc)

(2.54)

HI14
Fig. 14. Bulk nucleation field Hct as a function of the surface nucleation field H , of a
cylinder in a magnetic field parallel to its axis. The reference field H, is defined by H,=
&/2nu2 where do is the flux quantum. n is the number of fluxoids enclosed by the cylinder
.
at H , For n = 0 eq. (2.54) applies. For details see text. From Saint-James (1965).

The value of 1.33 in (2.53) was calculated from the intersection point of the
curves for n = 0 and n = 1 of fig. 14. Similar results were obtained by
Dalmasso and Pagiola (1965). In fig. 14 the value of HII+ Hc3 = 1.695HO2
when HII/Hr cv 1OOO. Hauser et al. (1974) obtained similar results for the
surface nucleation field of a cylindrical cavity.
CH. 6, 21 SMALL SUPERCONDUCTORS IN MAGNETIC FELD 461

2.4.2. Film in a magneticJieldparalle1to its surfaces

Ginzburg (1958) was the first to calculate the second order phase transition
field of a thin film

HscIH, = d Z 1 / d , (2.55)

where d is the thickness of the film. A thick film makes a second order phase
transition at Hc3 = 1.695 H c 2 . As for a thick cylinder Hc3 = H,, for K
< 0.417. For K > 0.417 thick films do not supercool,provided one neglects the
metastable surface sheath for K values between 0.407 and 0.595 as discussed
in 5 1.3.

6-

5-

I
3-

0 2 4 6 8 10 12
H/// H,
Fig. IS. ParaIleI nucleation field Ho = H I as a function of bulk nucleation field He, =
4,,/2nC2, normalized by the reference field H, = 1),/2nd', where d is the thickness of the
<
superconducting layer. Note that Hc2/H,= ( d / 0 2 where is the coherence length as
measured in the bulk. Equations which are good approximations are given for d / t < 1.7
and > 2.4. From Fink (1974).

Saint-James and deGennes (1963) were the first to calculate the size depen-
dent surface nucleation field of a film Hc3(d)= H I , which approaches eq.
(2.55) in the thin limit. It is shown in detail in fig. 15.

2.4.3. Cylinder in a magneticjeld transverse to its axis

Exact calculation of supercoolingand surface nucleation fields for arbitrary K
462 H.J. FINK ET AL. [CH.6,O 2

values and radii have not yet been published, but one would expect the critical
fields at which a second order phase transition occurs to be similar to those
of a film discussed in 5 2.4.2.

2.4.4. Sphere in a magneticfield

Surface nucleation and supercooling fields of spheres as functions of radius

for arbitrary K values have not yet been published. One expects results
similar to those of a cylinder in an axial field discussed in 5 2.4.1.

CRITICAL FIELD FOR TEMPERATURES BELOW THE LCP

2.5. THERMODYNAMIC

The thermodynamic critical field HT is defined as that field at which the Gibbs
free energy difference between the superconducting state and the (non-
magnetic) normal state is zero. This definition applies to all sample shapes.
HT = Hc(T)by definition when all dimensionsof a sample under consideration
are very large compared to A(T) and ( ( T ) .For a cylinder in an axial magnetic
field it follows from eq. (2.21) with g = 0 and g’ = 0 when Z2/Z0is expanded
for values of F,a $ 1 that (Esfandiari 1976)

HT/Hc = 1 +A/a. (2.56)

Near the LCP the appropriate solution for HTobtained from an approxi-
mation to higher order in Fo than given by eq. (2.22), and consequently from
a more complicated equation than eq. (2.41), is

(2.57)

Pr = 8/33 for a cylinder and eq. (2.57) is valid for 1 5 A t 5 33, or 2 / 3

5 a/A 5 10, to about 5 % or better accuracy, and for 4 3 5 a/A 6 4 to better
than 1% accuracy.
Figure 16 summarizes the various critical fields of a cylinder in an axial
fieldfora 4 <.

2.6. SUMMARY OF VARIOUS CRITICAL FIELD APPROXIMATIONS FOR OTHER

CONFIGURATIONS

The Gibbs free energy difference of a cylinder of radius a in a magnetic field

<
transverse to its axis is for a -4 (Ginzburg 1958)
CH.6,g 21 SMALL SUPERCONDUCTORS IN MAGNETIC F’IELD 463

(2.58)

The term connected with the magnetic field in eq. (2.58) is twice as large as
that in eq. (2.21), partially because the volume integral of the term lH-Hal ’
in eq. (2.2) outside the cylinder is not zero due to the nonuniform field dis-
tribution in a transverse field.
The Gibbs free energy difference of a film of thickness din a magnetic field
<
parallel to its surface is ford < (Ginzburg 1958)

(2.59)

<
and that of a sphere of radius r 4 (Ginzburg 1958)
!!= - F i + + q + f H : [ -
1- 3 coth (For)+----q .
V For (For)
3 1
Eqs. (2.21), (2.58H2.60) are written in GL normalized units. The critical
fields of a cylinder in a transverse field, of a film in a parallel field and of a
sphere are calculated from eqs. (2.58X2.60) in the same manner as that of a
cylinder in an axial field as shown above. All the pertinent fields are sum-
marized in tables 1 4 and in figs. 16-19. The figures show also the exact
solutions of eqs. (2.21),(2.58X2.60).

2.7. PENETRATION
DEPTH

For a bulk superconductor the measured penetration depth is defined by

eq. (2.45). Within the context of the GL theory 6(Ho) approaches A, defined
by eq. (2.7), as the applied magnetic field Ho approaches zero. Otherwise 6 is
larger than 1but at most d21 at H,,, for a bulk superconductor [eq. (2.49)].
In general, H(x) does not fall off exponentiallyexcept in the limit that Ho + 0,
in which case F(x) + 1 and eq. (2.15) is simplified.
For a slab of finite thickness din a field parallel to its surfaces, it is proper
to define an effective penetration depth 6(Ho,d) by

6(d) = -
Ho 0
H(x)dx, (2.88*)

where the surfaces of the slab are located at x = 0 and x = d. The superfluid
*Eqs. (2.61)-(2.87) are listed in tables 14.
 Table 1
Critical fields of a cylinder in an axial magnetic field

Eq.no. Equation Ref. Remark

(2.29)
(2.34
(2.33)
(2.30)
(2.52)
E
7c
(2.61)
(2.62)
(2.63)
(2.56)
(2.57)

[I] Ginzburg (1958). [2] Saint-James and DeGemes (1963). [3] Orsay Group on Superconductivity (1966). [4] Poulsen
and Fink (1974). [51 Rothberg Bibby et d. (1975). 161 Esfandiari (1976). [7] to about 5 % or better accuracy within
stated interval; for ref. see $2.8. [8] replace H, by Hzpfor T > TL.
 Table 2
Critical fields of a cylinder in a transverse magnetic field

Eq. no. Equation Ref.' Remark

(2.29)
(2.34)
(2.64)
(2.65)
(2.52)
(2.66)
(2.67)
(2.68)
(2.69)
(2.70)

~~

'For references see table 1.

466 H.J. FINK ETAL. [CH.6,# 2
.
N
II
.-
 Table 4
Critical magnetic fields of a sphere

E.q. no. Equation Ref.' Remark

(2.79) r/AL = J21/2 [l] r-radius; Lcp

(2.80) TL/Tc= 1 -21A2(0)/16r2 TL T.; r S €(O
N

(2.81) H,./Hc(0) = ( a / 2 ) ( l ( 0 ) / r ) f ; HL/Hc(TL)= 1- TL-Tc;r5€

(2.82) Hs.IHc(T) = J%A(T)lr [1,8] T c > T > T L a n d T S T L ; r / € 52
(2.52) HJH, = 2 . 3 9 1 ~ [2] K < 0.4172; r S C
(2.83) HJHC = [4/5(15)1/4](r/A)1/z [I] r/A 9 1; r < €
(2.84) HJHC = JZb{(A/r)'+(4b/21)[1-(21/4)
x (A/r)2]2}1/z
H*/Hc = 0.561/J~
HT/& = (2/3)'"(1+ 3A/2)
RT/Hc same as eq. (2.84) except B = 15/63
HT = He; usually enters intermediate state at
WJ3

'For references see table 1.

P
9
468 H.J. FINK ET AL. [CH. 6,5 2

velocity in the center of the slab, Q(+d), must be zero by symmetry and
therefore it follows that (in GL normalization) S(d) = - Q(O)/H,. This is
formally the same as eq. (2.45), however, the appropriate Q(0) value must be
obtained from an exact solution of the GL eqs. (2.14H2.16) for a slab of
thickness d.* No solutions of 6(d) have been published yet for arbitrary
values of dexcept those shown in fig. 10 which are valid ford $ 6.

3 .O I I I 1 I l l "

CYLINDER - A X I A L FIELD /.

r"
I
0
2.5

2.0
-

-
1
1.5 -

I
1.o 1 1 I 1
1 2 3 5 1 10 20

ah
Fig. 16. Shown are various critical field approximations for a cylinder of radius a in a
magnetic field parallel to its axis when a < <(TI.Numbers in parentheses are equation
numbers in the text and in table 1 ;sh means superheatingfield, T thermodynamic field, sc
supercooling field and LCP Landau critical point. The minimum is at all. = 3.8 and
H,,/H. = 1.59.

The GL theory, which is local, can be modified to take non-local effects

into account. Non-local effects will become of importance in a bulk super-
conductor when 6(H,,t) < 5, = fiuF/nd(0)where d(0) is one-half the BCS
(1957) energy gap at T = 0 K. For S 2 to,the local theory is applicable. In

* Boundary conditions:dFfdx = 0 at x = 0 and x = )d, and Q = 0 at x = )d.

CH.6,s 21 SMALL SUPERCONDUCTORS IN MAGNETIC FIELD 469

particular, very close to T, all superconductors become local since A(?)

approaches infinity.
Non-locality means that the current density i(r) at some point r depends
on the gauge invariant superfluid velocity Q(r') throughout a volume of
approximate radius toaround the point located at r. Pippard (1953) first
introduced this length by an analogy to the mean free path 1 as used in the

2.5

2 .o

\ EXACT ($h)\

<"
0
1.5
I

1.o
EXACT ( T )

(2.65) sc
(2.69) T

0.5
1 2 3 5 1 10 28

=/A
Fig. 17. Similar to fig. 16 except for a cylinder of radius a <( e(T) in a magnetic field
transverse to its axis. Equation numbers refer to table 2. The minimum is at all. N 3.8 and
HSh/H, 1.12.

work on the anomalous skin effect by Reuter and Sondheimer (1948) and
Chambers (1952) and Chambers' non-local extension (Pippard 1953).
tois the extent of a Cooper (1956) pair. It can be thought of as the smallest
size (-ti) which can be formed by a wave packet of superconducting
carriers in a bulk superconductor. More precisely, tois defined in the BCS
(1957) theory by the integralofthe kernelJ(Ir'-rl, t )

(2.89)
470 H.J.FINK ET AL. [CH. 6, !j 2

At r' = r the value of J is unity at t = 0 and decreases smoothly towards

I
zero as 1 r' -r is increased. Jvaries only slowly with temperature.
Consider some volume near the surface of a bulk superconductor. We know
that the superfiuid velocity Q,which is the response to a magnetic or electro-
magnetic field, varies significantly only over the distance 6(Ho) near the
surface when a magnetic field is applied parallel to the surface. If 6(Ho) 6 to
3 .O I I I I I I I I I

FILM

2.5

2 2.0
1

1.s

2.77) T
/EXACT (T)

1.o
1 2 3 5 7 10 20

d /A
Fig. 18. Similar to 6g.16 except for a film of thickness d Q C(T) with the magnetic field
parallel to its surfaces. Equation numbers refer to table 3. The minimumis at d / l = 4.55 and
H,,,lH. = 1.533.

then approximately only a fraction alto of the paired electrons within the
volume of the smallest-sized wave packet can contribute directly to the
supercurrent density. Thus, in the extreme non-local limit the effective number
density of carriers neftcontributing to the electromagnetic response in a bulk
superconductor is very approximately

For a non-local superconductor one can modify the GL theory simply by

replacing n in eq. (2.3) by some nea < n such as eq. (2.90). Alternatively, one
CH. 6,421 SMALL SUPERCONDUCTORS IN MAGNETIC FIELD 471

can derive from eq. (2.7), in analogy with the anomalous skin effect, an
effectivepenetration depth

Jeff N (A2tO)'? (2.91)

I lz/
YmIZ= Fz(0) such that their n,,
F2(O))'I3 and to eq. (1.3) for IC Q 1.
-
where 6(Ho) N A,, was used. Smith et al. (1970) "scale" n also by Y(0)
I nFz(0)S/t. This leads to A,, (A2to/ -

1 2 3 5 7 10 20

r/X
Fig. 19. Similar to 6g. 16 except for a sphere of radius r Q {(T).Equation numbers refa
to table 4. The minimum is at r/A = 5.24 and H&f, = 1.323.

From a practical point of view, when parameterizing non-local super-

conductors by experiments, it is probably simplest to retain definition (2.7)
for A and reduce !P,l I by an appropriate amount in relation to its local
value. This, from eq. (2.7), leads to larger values of A(0) than one would
obtain otherwise from the local theory and most likely to other temperature
dependences than given by eq. (2.36). This increase in A(0) is observed for
some materials, such as aluminium, whose measured A(0) value, as defined by
eqs. (2.7) and (2.36), is by a factor of 3.3 larger than the calculated local value.
472 H.J. FINK ET AL. [CH.6,$2

For moderately thin non-local films to which 6(Ho) < d << toapplies, we
suggest, when applying eq. (2.90) to modify the GL equations, that the value
of T o in eq. (2.90) be replaced by +d. Due to the boundaries of the film, the
range function J i n eq. (2.89) is spatially reduced. The smallest size of the wave
packet the superconductingpairs can form in one dimension is controlled by
the width of the film. Correspondingly more effective reduction of J should
occur in a thin cylinder and a small sphere. The effective penetration depth
corresponding to eq. (2.91) would then be thickness dependent and its value
would be approximatelyA,, N (+A’d)”’.
We suggest that for very thin non-local films to which d 6(Ho) 4 to
N

applies, both 6(Ho)and tobe replaced by +din eq. (2.90), so that in this case
-
neff n which is the approximate relation for a local superconductor. Thus,
in the very thin limit, all dirty superconductors whose mean free paths are
not limited by d should behave similarly to local superconductors.
The function x in eq. (2.3), defined by eq. (2.4), contains the mean free

n,, - --
path I and toso that other thickness dependences of 6(d) can be obtained.
For example, for very thin films to which 1 d 6 4 toapplies, x a d/to,
n, so that eq. (2.7) yields Ae, A((o/d)*’2,where A is the uncorrected
N

local value.
Non-local effects [eq. (2.90)], mean free path effects [eq. (2.4)], and effects
related to the reduction of the mean free path by boundary scattering (size
effects) are often difficult to separate clearly from each other in thin specimens.
In the latter case it is not possible to define a penetration depth as a single
material parameter, in general, which is independent of thickness and mag-
netic field. For example, for clean, very thin films in which I is limited by d,
eq. (2.74) for T > TLcan be written with ,Iecff = sA(<o/d)”2as (Toxen 1962;
Liniger and Odeh 1963; Douglas and Blumberg 1962)

H’JH, = fi4Aeff/d= s4zA(t0/d3)1t’, (2.74a)

where the constant of proportionality s depends on whether diffuse or specular

-
electron scattering is dominant at the specimen surfaces. Toxen (1962)
obtained s 4 4 2 , and Thompson and Baratoff (1968) s = 7z2/2/3 for
specular scattering, and Liniger and Odeh (1963) obtained s = 8 4 3 and
Thompson and Baratoff (1968) s = $11’ for diffuse scattering.
Tinkham (1958) suggested an effective penetration depth, which is related
to eq. (2.4) and takes empirically the mean free path and the thickness
dependences into account and which is to be substituted into the London eqs.
CH. 6,g 21 SMALL SUPERCONDUCTORS IN MAGNETIC FIELD 473

(2.91a)

Justifications for this approach are given by Ittner (1960) and a discussion is
given by Tinkham (1975).
A discussion in terms of Gor’kov’s Green’s function formalism is given
by Thompson and Baratoff (1968) who obtain results for extreme type I
superconductors (K 4 1) which are very similar to those of the GL theory
if 1 is replaced by 6. Assuming specular scattering at the surfaces, they obtain
for the LCP of a thin film d/dL n/1/2, and for T > TL the critical field
N

equation H2,/Hc(T) z n26/2d. These results are similar to eqs. (2.71) and
(2.74) within 0.7 % accuracy. Numerical calculations by Baldwin (1964)
based on non-local calculations by Liniger and Odeh (1963) lead to similar
results for diffuse scattering (H2,/HC(TL) = 2.27). Furthermore, due to the
anisotropy of the Fermi surface the penetration depth of a single crystal is
also anisotropic (e.g. Tai et al. 1975).
Unfortunately, none of the experimental data yet obtained is sufficiently
accurate and reliable to distinguish between the coefficients of the equations
for H2,/Hc(T)[eq. (2.74)] and d/6, [eq. (2.71)] given in previous sections and
those given in this section. The interpretation of experimental results has
usually been done in terms of the formulae summarized in tables 1-4, deter-
mining where necessary a size dependent penetration depth, e.g. d(d, 0), and
this is the approach that will be used in 8 4.

2.8. RECENT
THEORETICAL DEVELOPMENTS

Parr (1976c) calculated the superheating field for the semi-infinite half-space
by an analytic approximation. His result is

H,,/H, = (1 + 1 5 d ~ ~ / 3 2 ) / ( 1 / % ) ’ ~ ~ . (2.92)

Equation (2.92) is 2 % larger for K = 0.3 and 10% larger for K = 1.O than the
exact results.
Equations (2.57), (2.62), (2.67), (2.70), (2.76), (2.78), (2.84) and (2.87) near
the LCP were calculated by the authors as well as the exact solutions of Hsh
in figs. 18 and 19 and of HTin figs. 16-19. The latter solutions were obtained
from eqs. (2.21) and (2.58)-(2.60) by numerical procedures similar to those
used in obtaining the results of fig. 6 and discussed in detail in 9 2.3. Equation
(2.49), the data after eq. (2.50), eq. (2.51) and the theoretical results of figs.
5,12 and 13 are unpublished.
414 H.J. FINK ET AL. [CH. 6,#3

Rothberg Bibby et al. (1975) interpret their recent experiments on tin

whiskers (discussed in experimental detail in 8 4) by using terms up to order
F6 in the field-dependent term of the Gibbs free energy, and in doing so
point out that the zero-field GL equations should also contain a term of
this order for consistency in describing first order transitions. In the present
normalization there should thus be added to the right-hand side of eq. (2.22)
a term -3c I$ such that eq. (2.25) changes into
C = 11Hi~~/1024-~ (2.93)
and eq. (2.41) into

N(hi - dt)(99hi/128 - c/dt) = (h; - 1)’. (2.94)

The value of c can then in principle be obtained by a study of (h;-l)’/

@,-At). This was in fact found to approach zero at the LCP and hence
c was 99/128 at the LCP. This is surprisingly large for a term which is usually
neglected when compared, for instance, with Brandt’s (1973)series expansion
for the coefficient connected with this term. (His value of c is [31(5)/
4A2(3)](1-t)=0.681 (1 - t ) and in the experiments (1 - t ) N lo-’.) Since
the variables in eq. (2.94) are normalized with respect to HL and TL, the
accuracy with which c can be measured depends strongly on the accuracy
with which the LCP can be determined. Rothberg Bibby et al. (1975) used
the criterion of the presence or absence of hysteresis, and estimated relatively
small errors on their value of c. But if this criterion is doubted (as discussed
in $4) then the errors in c as determined in this way become far larger.
For the value of TL shown in fig. 5, for instance, the corresponding value of c
is perhaps zero, but probably negative. Further detailed experimental results
of H,(T) and HJT) near the LCP would be desirable.

3. Experimental techniques

In this section the preparation of moderately small superconductors and the

experimental methods used to detect their superconducting to normal phase
transitions will be discussed.
If the preparation method or experimental technique is widely known,
the reader will be referred to the original paper for details, and it will only
be where the technique is peculiar to this subject, or where knowledge of it
is helpful in understanding the experiments described in $94, 5 that any de-
tails will be given.
CH.6,O 31 SMALL SUPERCONDUCTORS IN MAGNETIC FlELD 475

3.1. SAMPLE
PREPARATION

3.1.1. CyIindersand whiskers

Doll and Graf (1967) prepared their microcylinders by extruding indium
from glass capillaries at a temperature several degrees below the melting
point in a helium atmosphere. The surfaces obtained were such that no
defects could be detected by a light microscope. These cylinders were too
large (7-122 pm) to be used for a study of the second order region, and their
superheating fields were lower than those subsequently found in spheres
(Feder and McLachlan 1968, 1969). McLachlan (197Oa, b) as well as Michael
and McLachlan (1974), prepared samples (2.8-10 pm) by forcing the
molten metal into glass capillary tubes. While the type I indium samples
(Michael and McLachlan 1974) also exhibited poor superheating, the type I1
indium bismuth sample (McLachlan 1970a, b) may well have shown ideal
superheating. This is probably because a defect, in order to act as a nuclea-
tion centre, must have dimensions of the order of e(T) and t(T)is much
smaller in type I1 materials than in type I.
Many experiments (Lutes and Maxwell 1955; Lutes 1957; McLachlan
1972; Rothberg Bibby et al. 1975) have been done on whiskers, which are
needle-like single crystals, capable of standing elastic strains of over 1 %.
They have the correct dimensions for doing size effect work as their mean
diameters are typically 0.5 to 2 pm.
The only successful method to date for preparing whiskers from super-
conducting materials such as tin, indium and their alloys is the extrusion
technique of Fisher et al. (1954), which results in whiskers of irregular cross
section (Bradley et al. 1957; Rothberg et al. 1971). The result of this is that,
although the cross section of the whiskers may be nearly constant along their
lengths, the theoretical formulae for circular cylinders are not strictly obeyed.
Ideal superheating is not observed in whiskers because the sharp edges or
protuberances resulting from their irregular cross sectionscanact as nucleation
sites. Such a sharp protuberance has even been observed to have a phase
diagram different from that of the rest of the whisker (Rothberg et al. 1971).
Whiskers have also been used to study dT,/dq (Davies et al. 1966) and
dH,/&, (Rothberg 1972) as they can stand elastic strains el of several
percent.

3.1.2. Films
Thin films are prepared either by vapour deposition in a vacuum or by rolling
476 H.J. FINK ETAL. [CH. 6 , $ 3

foils from the bulk material. The vapour deposition of thin films is a vast
field and as the techniques are well known they will not be gone into here.
It is, however, interesting to note that Caswell (1965) was able to vary the
amount of hysteresis observed by controlling the microstructure of his films.
For thicker ‘films’ (several microns and above), foils are to be preferred
as the mean free path in a rolled foil is generally much larger than in an
evaporated film of the same thickness. Also, a foil does not have the backing
which, due to differential thermal contraction, tends to distort and strain
films as they are cooled down.

3.1.3. Spheres
All the spheres made from low-melting point metals and alloys (Pb, Cd, TI,
Sn, In, Ga, Hg, SnIn and InBi) were prepared by the ultrasonic dispersion
of the molten metal in a suitably heated fluid. The resulting spheres, typically
1 to 100 pm in diameter, were separated into various size ranges usiug the
fact that they settle at different rates in a suitable fluid. Single spheres (see
for instance: Feder and McLachlan 1969; Parr and Feder 1973) were selected
from a given size range, whereas the powders were generally placed in an
inert dispersant so that the powder occupied some 5-10% of the totalvolume
(see for instance: Smith et al. 1970).
A different technique had to be developed for Zn and A1 because of their
high melting points (de la Cruz et al. 1971b). The molten metal was collected
at the end of a ceramic tube which was closed except for a small hole approxi-
mately 0.5 mm diameter. Drops of molten metal were then blown through the
hole into a dewar of liquid nitrogen where they solidified. The size spread
was 10 to 100 pm and the powders were sorted and dispersed as before.

3.2. MEASURING
TECHNIQUES

To detect the combination of magnetic field and temperature at which the

superconducting to normal transition takes place in the second order region
and at or near the LCP, a wide variety of techniques are possible. These
include resistive, tunnelling, magnetization, a.c. susceptibility methods and
microwave absorption. In the microwave absorption method (Di Crescenzo
et al. 1973) the surface-resistance derivative dR/dH was measured as a
function of the magnetic field parallel to the sample surface. The resistive
method, used by authors too numerous to mention, is the simplest and most
common, but as the electrical contacts can act as nucleation sites it is not
suitable for the study of ‘ideal’ superheating and supercooling. Tunnelling
CH.6,# 31 SMALL SUPERCONDUCTORS IN MAGNETIC FIELD 477

as used by Giaever and Megerle (1961), Douglass (1961a, b, 1962) and

Collier and Kamper (1966) is certainly the least ambiguous way of studying
the second order region and the LCP. However, the preparation ofthe samples
is more difficult and the technique has so far been limited to thin films.
It is also apparently not suitable for the study of superheating and super-
cooling as the junctions and/or strains in the sample act as nucleation sites.
In order to study superheating and supercooling well below the LCP, it is
necessary that the sample be mounted in a strain-free manner and that no
contacts be made to it. This necessitates the use of a magnetic or susceptibility
method. The disadvantage of these techniques is that the signal becomes
extremely small near the LCP, or in the second order region where u/A is of
the order of 1 or less. This means that accurate measurements of T,are not
possible. For this and other reasons many authors have used a combination
of techniques such as tunnelling, resistance and magnetization (Burger et al.
1965); resistance and magnetization using a torque magnetometer (Robinson
1966); a.c. susceptibility, magnetization and resistance (Miller and Cody
1968); a.c. susceptibility and resistance (Pellan et al. 1973).
All the recent experiments designed to study ideal superheating and super-
cooling, with the exception of Doll and Graf (1967) (who use a He magneto-
meter), use an a s . susceptibility method. In the original powder work of
Feder et al. (1966a) the sample (a 1-5 pm indium powder) was placed in the
r.f. coil of the tank circuit of a marginal oscillator and the change in the
oscillator frequency was plotted on an XY recorder as a function of applied
field at various temperatures. This method has been successfully used in
many subsequent experiments.The Brown University group (see for instance:
Smith et al. 1970) measured the change in the low frequency magnetic
susceptibility in superconducting powders using an electronic mutual
inductance bridge.
As a considerable part of $5 will be devoted to superheating and super-
cooling in single micro-particles (spheres, whiskers and microcylinders),
the little known method developed for and used in virtually all experiments
of this type will be briefly discussed here. The sample is mounted in as
strain-free a manner as possible in the secondary of a micromutual induct-
or. The voltage output from the secondary is stepped up by a factor of about
700 by a transformer located in the helium bath, and the output of the trans-
former is connected to the input of a low noise lock-in amplifier. In a typical
setup (McLachlan and Feder 1968) the residual resistance of the secondary
inductor was of the order of 0.1 and hence the resistance seen at the input of
the lock-in amplifier was of the order of 50 OOO 61, which is about optimum
478 H.J. FINK ETAL. [CH.6,# 3

at the frequency of 140 kHz used in these experiments. In this way a noise
level of 2 . 0 ~lo-" V was achieved (using 8 0.3 sec time constant), which
enabled the change in signal of about lo-'' V,caused by the transition of a
single microparticle, to be observed (McLachlan and Feder 1968, 1969).
The pick-up coils (secondaries) had to be designed so that the sample had a
reasonable fill factor. For spheres (Feder and McLachlan 1969; Parr and
Feder 1973) this was done by twisting an insulated piece of 15 pm copper
wire in the fingers until a vanishingly small (H 50 pm dia.) loop was obtained
at the end. This was then lacquered down onto a plexiglass disc, as was the
primary or drive coil, which consisted of a pair of parallel wires passing
close to the pickup coil. On the other hand, whiskers (McLachlan 1972)
were laid in the groove formed by two touching parallel 15 pm wires and
the drive wires crossed the pickup wires at right angles near both ends of
the 1.0-2.0 mm long whiskers. The microcylinders (McLachlan 1970a, b;
Michael and McLachlan 1974) were long enough to place in one secondary
coil of a conventional concentric mutual inductor, the secondary of
which consisted of two nearly equivalent coils (I.D. 200pm) connected in
series opposed. However, as the cancellation of the series opposed coils
was insufficient, a bridge circuit had to be used to further cancel the back-
ground signal.
The drive or a s . magnetic fields at the surface of the superconductor
usually of the order of 0.1 G which, if parallel to the static or swept magnetic
field, can have considerable influence on the observed and H,, as H,,,=
- H(peaLa.c.). This can, of course,
H(static) -k H(pcak a.c.) and H, =H(static)
be taken into account by measuring Hubor H,, for a number of different a.c.
fields (currents) and extrapolating to zero field. To overcome this the static
and a.c. magnetic fields are sometimes placed at right angles to each other,
which considerably reduces the vector sum of the two fields and hence the
effect on Hnhand Hat.
The signal S(T, H), in a reversible region, measures the derivative of the
magnetization M-HV,,,, where V,,,is an effective volume, and hence

If the amplitude of the a.c. field is small compared with the static field
and they are at right angles to each other, dV,,,/dH=O to first order, because
the scalar value of the total field does not change. Hence
CH.6,# 41 SMALL SUPERCONDUCTORS IN MAGNETIC FIELD 479

As the second term dominates, especially near Hsh,it is necessary to use a

parallel field geometry when attempting to observe the change in 6(T, H)
with magnetic field (Parr 1975). The above considerationsapply to both single
particle and powder samples.
In order to measure the various critical fields of interest, a hysteresis loop
at constant temperature is obtained by slowly sweeping the magnetic field
up and down. In order to obtain good supercooling the magnetic field must
be taken to a high enough value to drive the entire sample normal, as tiny
residual pockets of superconductivity can act as nucleation sites when the
field is decreased. Similarly, to obtain good superheating, the field must
first be decreased to a point where the entire sample is superconducting.
The temperature is usually stabilized, using an electronic feedback device,
and measured using the vapour pressure of the helium bath or a germanium
thermometer.
In order to enhance the superheating and supercooling observed in cylin-
ders or whiskers, an inhomogeneous d.c. field is often used to eliminate
nucleation at the ends of the specimen. This has been done by Faber (1957),
Doll and Graf (1967), McLachlan (1972) and Michael and McLachlan (1974).
In all cases considerable enhancement of the superheating or supercooling
field was observed, but except for supercooling very close to To,the ideal
values of the superheating and supercooling fields were not observed. For
the exact coil configurationsused, the reader is referred to the above papers.

4. Second order phase transitions and the Landau critical point

4.1. INTRODUCTION
In this section we deal primarily with the experimental predictions of $2.2,
that is the second order region and the LCP. The experimental verification
of some of the thermodynamic predictions as well as tunnelling results to
show directly the variations with temperature and magnetic field of ILII’,
which is proportional to l+lz, will also be discussed. The variation of H,JH,
with sample size is dealt with at the end of this section.
The following section ($5) deals primarily with superheating and super-
cooling in the region where the moderately small specimens are behaving
as bulk or nearly bulk specimens. (It is only in moderately small specimens
400 H.J. FINK ETAL. [CH.6,O 4

that significant superheating and supercooling have been observed.) This

division into two sections is not purely arbitrary, since specimens which are
small enough to have an experimentally accessible second order region do not
exhibit optimum superheating at lower temperatures even in experiments
specificallydesigned to observe this (see McLachlan 1972; Pellan et al. 1973).
The samples which exhibit the largest superheating and supercooling are
in the 10-50 pm range and their second order regions extend over too limited
a temperature range to be accurately studied.
The criterion usually used to distinguish between first and second order
transitions, that is the presence or absence of hysteresis in the phase transi-
tion, needs clarification as it is a source of ambiguities and possible errors.
The problem does not lie in the methods used to distinguish between the
normal and superconducting states (see 4 3), but rather in the fact that most,
if not all, samples do not exhibit the maximum predicted superheating and
supercooling in the first order region (Baldwin 1963 and fig. 5). An example
of the type of data obtained is shown in fig. 20 which shows the hysteresis
in the resistive transitions obtained by Rothberg Bibby et al. (1975). These
data have been chosen for presentation as they are the clearest of the very
few cases where all three fields (HT, H,,, Hsh)are seen in the same sample.
However, it will be seen there was no superheating field just below the LCP
(fig. 20), although as fig. 21 shows there was probably ideal supercooling
as the supercooling field is an extension of the second order critical field
[eq. (2.30) for axial cylinder]. On the other hand Baldwin (1963) concluded
+
that he was only observing of the predicted supercooling. These observa-
tions illustrate the fact that the hysteresis observed may be ambiguous and
depends on the sample. Further, it must always be borne in mind that the
lack of hysteresis does not guarantee a second order transition.

4.2. BEHAVIOR
OF THE ORDER PARAMETER

I I
Since the square of the modulus of the energy gap A is proportional to the
I I
square of the modulus of the order parameter $ a measurement of Id I
by tunnelling provides the most direct experimental evidence of a second
order phase transition.The tunnellingexperiments of Douglass (1961a,by1962)
and Collier and Kamper (1966) distinguish clearly between first and second
order transitions. Figure 22 shows how the energy gap for a 3000 A aluminium
film,in aparallel field,wasobserved to go continuouslyto zero asHapproached
I I
H,, while in a 4OOO A film there was an abrupt change in A * at H, indicating
a first order phase transition. Unfortunately, none of these authors made a
CH. 6,841 SMALL SUPERCONDUCTORS IN MAGNETIC FIELD 48 I

detailed study of the validity of the equations given in $2. But Douglass'
(1961) data are consistent with a LCP at a film thickness which has the pre-
dicted value of 2 / 5 times the penetration depth.
3.866 K

I I I I 1 1
0 8 16
H (gauss 1
Fig. 20. Recorder tracings showing the measurement of the various critical fields at a
fixed strain (0.35%) at gradually reduced temperatures near T,(e) for a [OOI] whisker. The
double-headed arrows ($) indicate the reversible transitions corresponding to Hz,(7'. e)
above the LCP and HT(T,e) below the LCP. The single headed arrows indicate the irrever-
sible superheating(t ,H.h) and supercooling(1,H,J transitions which occur below the LCP.
(Reproduced from Rothberg Bibby et al. (1975) by courtesy of The Royal Society.)

Thermal conductivity measurements can also be related to Id I * and hence

I@
to I '. The experiments of Morris and Tinkham (1961) show, for example,
how the thermal conductivity was observed to go smoothly to its normal state
value as H tended to H, for a second order transition in a 700 A tin film,
while the transition was abrupt for a first order transition in a 2800 A film.

4.3. FIRST
AND SECOND DERIVATIVESOF THE FREE ENERGY

The change in the Gibbs free energy of a superconductor with temperature T,

482 H.J. FINK ETAL. [CH. 6.0 4

applied magnetic field Hand uniaxial stress o1is given (Seraphim and Marcus
1962; Rothberg Bibby et al. 1975) by

1 (K)
Fig. 21. Graphs of Hi, (2'. e) [a], (a
H z (T,e) ( 0 )and H i (T, e) as functions of the
temperature T and the strain e for a [Ool J whisker. Note that the same straight line can be
drawn through the supercooling and second order critical field points and that To(e) i s a
linear function of the strain for this orientation. Data from Rothberg Bibby et al. (1975).

The last term becomes + Y dP if hydrostatic pressure P is applied, where V is

the volume. The entropy S,magnetization M and the generalizeddisplacement
Vq (q being the ith component of the strain) are thus first derivatives of the
Gibbs free energy, and the latent heat is related to S.Derivatives of these quan-
tities are the second derivatives of the Gibbs free energy, and are quantities
such as the specific heat, thermal expansion and elastic moduli.
The order of a thermodynamic phase transition is defined in terms of the
behaviour of these derivatives of G (Ehrenfest 1933; Pippard 1957). Accord-
ingly, as the temperature is increased through the LCP the changes, A"" (at the
CH. 6,o 41 SMALL SUPERCONDUCTORS IN MAGNETIC mELD 483

normal-superconducting transition) of first derivatives of the Gibbs free

energy are no longer finite but are zero; but the second derivatives of the
Gibbs free energy now show finite discontinuities.
Due to the divergence of A(T) at To all superconductors, no matter how
large, pass through their LCP as the temperature is increased, and hence
undergo a second order phase transition before reaching To.That the super-
I.Og, I 1 1 I I 1 I 1 I '
\ 0
I
I
- A \\ -1 I '
\ o
\\ I
I
0.8 - A\\
\
0

N
- \\ A
\
\ I
\ I
I
'\ I -
'O\ I

'y,
- \\
\
L
a a\\
* 0.4- \
I
6
(2:
W - ALUMINUM \
I
I -
I

- 0.2-
2
W APPROX. REDUCED d
SYMBOL THICKNESS TEMP. \\A
I
I

A 3000-A 0.745 1-9

9-
- 0 LOW A 0.774 3.5
\ I
I I I 1 I I I I
I \I
0,

Fig. 22. Energy gap of aluminium vs. magoetic field for films of t h i c k 3000 A and
4OOO A. The dashed curves are the best straightlines through the data points. After Douglas
(1961b).

conducting transition at T, is of second order was in fact first suggested

from measurements of the specific heat (Keesom and Kok 1932) since these
show a finite discontinuity and there is no latent heat associated with phase
transition at T,.In general, it is the absence of a latent heat which makes
second order phase transitions reversible, while first order phase transitions,
which have a latent heat associated with them, may be hysteretic.
Measurements at T, have been made on the specific heat discontinuity
A " T H = 0 by Corak and Satterthwaite (1956) and Cochran (1962) and on the
484 H.J. FINK ET AL. [CH.6,# 4

thermal expansion discontinuity dn*aby Andres (1964) and White (1964)

while changes in the elastic moduli for polycrystalline and single crystal
samples have been observed by Landauer (1954), Grassman and Olsen (1955),
Welber and Quimby (1958) and Gibbons and Renton (1959). These quantities
(second derivatives) are interrelated because of the Ehrenfest relations, as
shown for a superconductor under hydrostatic pressure by Pippard (1957).
For single crystals under elastic strain Rothberg Bibby et al. (1975) found that
the Ehrenfest relation

where s,, denotes the compliance tensor, was satisfied within the experimental
errors quoted by the individual authors. Unfortunately there were insuillcient
experimentaldata available to test the other Ehrenfest relations.
By contrast, when the transition is of first order there is a change in first
derivatives of the Gibbs free energy at the transition, such as the volume
(Olsen and Rohrer 1956), or the length (Ott 1974). Since 'An'G = H,?/8n, the
thermodynamic approach also predicts relations between first derivatives and
some features of the critical field curve; for example volume changes are
related to dHc/dP.
It is therefore possible in principle to observe the change of order of the
transitions of a moderately small superconductor at the LCP by measurement
of any of the first and second derivatives of G; unfortunately, except in the
case of magnetization and susceptibility, such measurements have not yet
been performed.
If pressure P or uniaxial stress oi is regarded as a third thermodynamic
variable in addition to H and T then the phase diagram becomes a second
order transition surface, bounded by T, (al), by H,(T,o,), and by a Landau
critical line. Such a surface was proposed by Hake (1968, 1969) for the second
order transition at Hc2 of a type I1 superconductor but has not yet been
experimentally observed. However, Rothberg Bibby et al. (1975) have observed
(fig. 21) a similar surface in the transitions of elastically strained tin single
crystals (whiskers) and have, where possible, applied the Ehrenfest equations
with two independent variables, which relate the surface to the second
derivativesof the Gibbs free energy.
Magnetization M is a first derivative of the Gibbs free energy so that the
behaviour of M and dM/dH, often used in studying the superconducting
transition, is different at first and second order transitions. A formula for
dM/dH for a cylinder, derived from the GL theory in the second order region,
CH.6,# 41 SMALL SUPERCONDUCTORS IN MAGNETIC FIELD 485

is shown to be reasonably well obeyed by Michael and McLachlan

(1974).

4.4. CRITICAL FIELD MEASUREMENTSIN THE SECOND ORDER REGION

The thermodynamic critical field in the second order region is given by eqs.
(2.30), (2.65), (2.74), (2.82) for axial and transverse cylinders, films and spheres
respectively, but as no thorough measurements have been made of second
order transitions of spheres or transverse cylinders this article will concentrate
on axial cylinders and films. For these the equations are
Axial cylinders: Hzp/Hc(t)= 4L(t)/a, (2.30)

Films : Hzp/Hc(r)= dZA(r)/d. (2.74)

Using the temperature dependences H,(T) = H,(O) (1-tZ) and Az(t)

= Az(0)/(l- t 4 ) the expected temperature dependence of Hzp is [(l - t 2 ) /
(1 + t z ) ] ’ l z which becomes (I - t)”’ very close to T,.
At this stage it should be pointed out that another type of second order
superconducting-normal transition exists for “bulk” samples with K greater
than 0.417. (See for instance Cody and Miller 1968; Di Crescenzo et‘al. 1973;
Maloney et al. 1972). This transition is the appearance of the surface sheath
at H c 3 . However, it is not easily confused with Hzpas it has a different
temperature dependence, namely (1 - t Z ) / ( l + t 2 ) , and can usually be dis-
tinguished from Hzp by the experimental procedure. Although this H,,
is related to If,, below K = 0.417, it will not be dealt with in this article.
Lutes (1957) and Rothberg Bibby et al. (1975) (fig. 21) have 3bserved in
whiskers with the magnetic field parallel to the axis that H2pdoes indeed have
a temperature dependenceof (1 - f)’I2 close to T,.The latter authors have also
shown (figs. 5 and 21) that at temperatures immediately below the LCP, H,,
has the same temperature dependence as Hzp,as predicted in § 2. As whiskers
are not circular in cross section, eq. (2.30) cannot hold exactly. This, coupled
with the fact that the small and irregular cross section make it impossible to
determine an exact value for a, rules out the possibility of obtaining exact
values of &a, 0) or A(0)from these measurementsalthough the values obtained
by Rothberg Bibbyet al. (1975) are reasonable.
For films in parallel fields, where eq. (2.74) should hold exactly, Hzp has
been studied or observed by many workers (see for instance: Zavaritskii
1951; Sevast’yonov 1961; Appleyard et al. 1939; Khukhareva 1962, 1963;
Toxen 1962; Baldwin 1964; Burger et al. 1965; Cody and Miller 1968, 1972;
B
486 H.J. FINK ET AL. [CH.6 , 8 4

Miller and Cody 1968; Maloney et al. 1972; Di Crescenzo et al. 1973; Pellan et
al. 1973). Many report, directly or indirectly, observing the temperature depen-
dence [(l- t 2 ) / (1 + t 2 ) ] 1 / 2for H2p.However, the values of A(0) obtained from
eq. (2.74) were in all cases different from that for the bulk material. For in-
stance, Sevast’yonov’s (196 1) torque magnetometer measurements on tin and
indium films (thicknesses 300-5000 8) show qualitative agreement with eq.
(2.74) but thevalues obtained for A(0)are higher than that for the bulk material.
Khukhareva (1962, 1963) found similar results for freshly deposited and an-
nealed aluminium and mercury films. These and other more recent results (see
below) show that the correct penetration depth to use in interpreting these
results is not A(0) but the size dependent 6(d, 0) discussed in 3 2.7. In evap-
orated films the shorter mean free path is at least partially due to the evap-
oration process, but this will be treated as a “bulk” property, as we are
interested in the effect that the size of the specimen has on the mean free path
and hence on 6 (d, 0).
In the extreme case, discussed in 3 2.7, when d I 6 < to5 I
N N the
effective penetration depth becomes 6 (d,O) = sA (50/d)112(see 3 2.7), and H Z p
should be proportional to d-’I2 as predicted by eq. (2.74a). Experimental
confirmation of this thickness dependence was found by Toxen (1962) in pure
indiumfilms,whose thicknesseswerelessthanabout 20008. A d- 3/2dependence
for HZpwas also found by Burger et al. (1965) for tin films in this size range,
whereas Baldwin (1964) found H Z pvaried as d - P where IpI 2 1.25. Toxen’s
(1962) work was extended by Toxen and Burns (1963) to include impurity
mean free path effects as well as size effects and was applied to the critical
field data measured on In Sn alloys.
In thin films of lead (Cody and Miller 1968,1972) and tin (Miller and Cody
1968) eq. (2.74) was found to be obeyed quantitatively only if a size dependent
penetration depth was used. The size dependent penetration depth used was
a modification of that given in 5 2.7, namely

where l/leff= 1/1+ l/d and lis the “bulk” mean free path.
A similar increase in the penetration depth with decreasing thickness has
been observed in the recent microwave measurements by Di Crescenzo et al.
(1973). The results of Di Crescenzo et al. (1973) for H2,/HCand HT/Hc are
shown over a large range of A(t)/d,or rather 6(d, t)/d,in fig. 23. The agreement
with theory in the second order region is excellent. The results of Pellan et al.
(1973), shown in fig. 1, also show good agreement with theory.
CH. 6,841 SMALL SUPERCONDUCTORS IN MAGNETIC FIELD 487

CRITICAL
4.5. LANDAU POINT
As discussed in 3 2 the LCP is given by the conditions specified in eqs. (2.29)
(2.71) and (2.79) for axial and transverse cylinders, films in parallel fields,
and spheres respectively. As virtually all meaningful work has been done
on axial cylinders and films, attention will again be focussed on these geo-
metries. The conditions for the LCP are:

Axial cylinders: a/l(T,) = a l l L = 4 3 , (2.29)

Films: d/l(T,) = d / l L = 4 5 . (2.71)

, , , I , . . . .
a 7000 A
A 11c4l '.
0 3600 I'

+ 3000
2800 "

0 2500
* 1700
0 1000 "

x 700 .'

-'

d/S ( t . d I

Fig. 23. H2,/Hcabove the LCP and HT/Hcbelow the LCP plotted as a function of d/d(r,d).
The experimental results are those as shown in fig. 7 of Di Crescenzo et al. (1973)and the
theoretical curve is that given in fig. 18. HT/Hcas given by the exact theory is slightly larger
than the interpolation used by Di Crescenzo et at. (1973) over most of the range of
dl6 0 , d ) .

When eqs. (2.29) and (2.71) are combined with eqs. (2.30) and (2.74) respec-
tively the following equations valid at the LCP,are obtained:

Axial cylinders: HL/Hc(TL)= 2.3 1, (4.1)

Films : HL/Hc(TL)= 2.19. (4.2)

Experimentally the LCP is usually obtained by extrapolating H,,, Hsh

and/or HT back to the point where they intersect, that is, where hysteresis is
first observed. As previously mentioned the hysteresis observed is seldom
488 H.J. FINK ETAL. [CH. 6,g 4

ideal which can make this way of identifying the LCP questionable. A further
problem, as mentioned in $2.7 and 54.4, is that the penetration depth A(0)
appearing in the equations is affected by the thickness of the samples so
that it is difficult to make a quantitative test of the formula for the LCP. How-
ever, since A(or 6 ) has been eliminated in eqs. (4.1) and (4.2) some of the pre-
dictions of GL theory can be tested without knowing exactly what A(0) or
6 (d, 0) is under these circumstances.
As previously mentioned, Douglass’ (1961a, b) data are consistent with a
LCP at a film thickness which has the predicted value of 4 5 times the pene-
tration depth [eq. (2.71)], although his experimental points only bracket this
value and none are taken very close to the critical conditions.
For films, Baldwin (1964) and Caswell(l965) found no hysteresis if H / H c
was greater than N 2.19 and for whiskers Lutes (1957) found no hysteresis
for H/H, greater than N 2.31. Although the scatter of the data points makes
exact determination of the LCP impossible, these measurements may be
taken as qualitative verification of eqs. (4.1) and (4.2).
Rothberg Bibby et al. (1975) also working on whiskers, were able to dis-
tinguish between superheating, supercooling and thermodynamic transitions
using a switching technique described by Rothberg et al. (1971). They also
knew that they had maximum supercooling since (as shown in fig. 21) eq.
(2.30) was obeyed; their measurements were close enough to T, that super-
cooling at H c 3 ,if relevant, would give the same temperature dependence as
that at H,, (see Tilley et al. 1966). The results of Rothberg Bibby et al. (1975)
were analyzed using as a criterion for TL the presence or absence of hysteresis
if T c T L or T > TL respectively. The behavior of HT was discussed using
terms up to order F6 in the GL equations, as discussed in 4 2 above, and a
refinement, using terms up to order F * , was discussed by Nabarro and
Rothberg Bibby (1975). The major problem which led to this new analysis
was that the observed HT(T) values seemed to approach Hsc(T)at a finite
angle at this value of TL. An alternative analysis of the same data has been
carried out by one of the present authors (HJF) with a higher value of T L ;
that is, making the assumption that there was no hysteresis at temperatures
just below this value of TL even though the transition was of first order.
Behavior of this kind might perhaps arise because whiskers are far from ideal
cylinders. Excellent results are obtained by such an analysis, as shown in
fig. 5, and it should also be noted that the values of(HL, TJ used in this ana-
lysis then obey eq. (4.1). As shown in fig. 20, Rothberg Bibby et al. found that
the onset of hysteresis was usually in the form of supercooling; superheating
began at lower temperatures.
CH.6,O 51 SMALL SUPERCONDUCTORS IN MAGNETIC FIELD 489

The non-existence of a superheatingfield just below the LCP has also been
observed in whiskers by McLachlan (1972) and in axial and transverse
cylinders (Michael 1973; Michael and McLachlan 1974). The reason for this
is at the moment unknown.
Michael (1973) has also observed that the onset of second order phase
transitions in both axial and transverse cylinders occurred at the same re-
duced temperature as predicted by eq. (2.29). Similar results are reported by
McLachlan (1972) for whiskers but as the cross sections of whiskers are
irregular these results are less conclusive.
Di Crescenzo et al. (1973) have obtained TL in three different ways from
their results on Pb films and found the resulting TL’sto be in excellent agree-
ment. Their methods are:

(i) Directly from eq. (2.71), using a value of 6(d, 0) obtained from other
measurements.
(ii) From the temperature at which the condition given by eq. (4.2) is
satisfied.
(iii) From the point where their microwave absorption peaks change shape
indicating a shift from a first to a second order transition.

The internal self-consistency of their results is an excellent verification of the

theoretical predictions made in $2.

4.6. THERMODYNAMIC
CRITICAL FIELD

The best experimental results for the thermodynamic critical field as a

function of size are those of Pellan et al. (1973) shown in fig. 1 and Di Crescenzo
et al. (1973) shown in fig. 23. In fig. 23 the results of Di Crescenzo et al. (1973)
are plotted together with the results from 5 2 shown in fig. 18 and not the
interpolation formula used by these authors. As can be seen in both cases the
agreement between the theory and experiment is excellent, even in the inter-
mediate ranges of d/d.

5. First order phase transitions- superheating and supercooling

5.1. INTRODUCTION

In this section the objectives will be firstly to evaluate the results obtained in
superheating and supercooling experiments in terms of the equations given in
490 H.J. FINK ET AL. [CH.6, $ 5

tj 2, which are summarized in the phase diagram shown in fig. 2, and secondly,
to examine the change in the superheating and supercooling fields as the LCP
is approached. It is necessary to discuss superheating and supercooling first,
as one cannot expect results like those shown in fig. 1 unless the sample is
exhibiting nearly ideal superheating and supercooling. In fig. 2 it can be seen
that the most important parameter in superheating and supercooling is K ,
and from figs. 1,7 and 8 it can be seen that this is also a dominant parameter
in the determination of how the superheating and supercoolingfields approach
the LCP. For instance, if the K value becomes large Hs,/Hc should not
exhibit a minimum as a function of a/A. We will therefore examine the ‘bulk’
superheating and supercooling results first and then the evidence for size
effects in each range of K. However, it is first necessary to make some general
observations regarding superheating and supercooling. Previous review
articles on this subject are Burger and Saint-James (1969) and Burger (1969).
Experimentally, supercooling is relatively easy to observe, whereas large
superheating is difficult to observe in bulk specimens. Supercooling was first
studied systematicallyby Faber (1957), who found that by locally lowering the
magnetic field applied parallel to a cylinder of a type I material such as Sn, In,
or Al, he could keep the specimens in the normal state at fields much lower
than the bulk critical field Hc(T).The relative amount of ‘supercooling’thus
obtained varied significantlyas a function of the position of the field coil along
the specimen, and it was proposed that certain flaws and defects near the
surface of the specimen acted as nucleation centres for the superconducting
phase. It was also observed that the effect of the flaws seemed to decrease as
the critical temperature was approached. This is to be expected if one assumes
that the flaws have dimensions such that they become of negligible size com-
pared to r(T) and A(T) near T,. Therefore, very close to T, the supercooling
observed should be typical of the material and not of the defects, and useful
information can be expected from the results.
The first results on superheating were obtained by Garfunkel and Serin
(1952), but large superheating, as well as supercooling, was first observed
(Feder et al. 1966a) in samples consisting of a large number of indium spheres
having diameters in the range 1-5 pm. Similar experiments have since been
performed on other materials. The reason for this success is that the chance of
having a defect that will act as a nucleation centre decreases with sample size.
Also, when a phase is nucleated in one sphere, it will not propagate to the
others. The drawback with experiments on powders lies in the fact that one
observes relatively smeared-out transitions, which makes the final interpre-
tation of superheating and supercoolingfields somewhat arbitrary. This non-
CH. 6,$ 5 1 SMALL SUPERCONDUCTORS IN MAGNETIC FIELD 491

ideal behavior is caused by variations in size, shape, and quality of the spheres,
as well as clustering and other effects that can distort the magnetic field seen
by some spheres.
Most of the above disadvantages were first overcome by Feder and
McLachlan (1968, 1969) who studied superheating and supercooling in
selected single spheres. The advantagesare:

(i) The sample can be selected for size and quality under a microscope and
in the case of a metal coated sphere, used in experiments to study the
suppression of the surface sheath, the coating can be checked to see if it is
continuous.
(ii) The superheatingand supercooling transitions are sharp and unambigu-
ous; indeed it was only after the publication of results for single
spheres that it became clear which points on the hysteresis curves for
powders actually corresponded to the superheating and supercooling
fields, so that the powder data could be correctlyinterpreted.
(iii) An accurate demagnetizing coefficient taking into account the finite
penetration depth 6(T, H ) can be obtained.
(iv) The variation of 6(T, H ) with magnetic field can also be measured and the
only measurements of 6(T, H ) in strong (H -,Hsh)magnetic fields have
been obtained from single spheres (Parr 1975,1976a).
(v) The magnetic field and sample can be rotated with respect to each other
and information can be obtained about the nucleation sites causing pre-
mature transitions from the metastable states.

As better and sometimes unique data can be obtained from single sphere
measurementsthis review will where possible concentrate on the data obtained
in this way. For more details on the results obtained from powders the reader
is referred to Smith et al. (1970).
In spite of the use of inhomogeneous magnetic fields to eliminate nucleation
at the ends of the cylinders, really good superheatinghas never been observed
in type I microcylinders (Doll and Graf 1967; McLachlan 1972; Michael and
McLachlan 1974). Greater success has been obtained with a type I1 micro-
cylinder (McLachlan 1970b). The superheating results from films (fig. 1 and
Pellan et al. 1973) also do not exhibit anything like ideal superheating.
The results of superheating and supercooling experiments are usually
given in terms of Ginzburg-Landau bulk formula derived in 6 2, i.e.,

H,,(T) = H,,(T) = 2.397 KH,(T) (2.52)

492 H.J. FINK ETAL. [CH.6, # 5

and
H,,(T) = Hc(T)/(K1/2)"2 K 4 1. (2.63)

Although these results strictly apply only for local electrodynamics near T,,
these formulae are used to parameterize the results over the entire temperature
range and we define

For a spherical sample it has been customary to multiply the observed super-
heating field by +,to take into account the fact that on the equatorial band of
+
the sphere, the field is times larger than the applied field. Hence for a sphere
K,h is defined as

K&") = 0.3143Ht(T)/Hfh(T). (5.3)

However, close to T,,Parr and Feder (1973) have found it necessary to take
into account the finite penetration depth of the magnetic field. The local
equatorial field He, parallel to the surface of a sphere (radius r) as given by
London (1950) is

Therefore, for small A/r Parr and Feder (1973) defined as

where A(0) is the appropriate penetration depth at zero field and

y = [l -(T/Tc)4]-1/2 is the well-known phenomenological temperature
dependence of A(T).
In order to calculate K,h or K,, it is necessary to know H,(T). As it is in most
cases impossible to measure H,(T) in the same sample, it is normally calcu-
lated from the formula
CH.6,O 5 J SMALL SUPERCONDUCTORS IN MAGNETIC FELD 493

where H,(O) is the bulk critical field at absolute zero and D is the function
givingthe deviation from parabolicity(e.g., Mapother 1962). Asmanymeasure-
ments are made extremely close to T,, the value of H,(T) and hence K(T)is
extremely sensitive to the exact value of T, used in the above formula. As T,
cannot usually be obtained accurately from the experimentalresults it must be
chosen so as to give self-consistent results for ‘csh and icSc. The value chosen is
invariably, within the experimental error, consistent with the accepted value
of T, . For details as to how T, is actually determined see Feder and McLachlan
(1969) and Parr and Feder (1973).

5.2. Low K TYPE I COATEDAND UNCOATED SUPERCONDUCTORS

A typical curve for the susceptibilityof an isolated low K single sphere is shown
in fig. 24. The depression in the diamagneticsusceptibility as Hshis approached
is due to the increase of 6(T,H ) with magnetic field and is only readily observed
when the small alternating magnetic field is parallel to the static field.
The variation of K,,, and ci, with the angle between the magnetic field and
the sample is shown for an indium sphere in fig. 25. Virtually no correlation
was found between the directions of greatest superheating and greatest

I I I I I I

Sn sphere 15.4 pm
Tll,: 0,9961

I I 1 I I I

MAGNETIC FIELD (Oel

Fig. 24. The off-balance signal from the detection system plotted as a function of the
magnetic field for a 15.4 ,urn diameter So sphere. The a.c. field is parallel to the static field
and the depression of the signal close to H,,, is due to the field dependence of the penetration
depth. The effect is almost undetectable if the a.c. field is at right angles to the static field.
The positions of H.h and H,, are clear and unambiguous.After Pam (1976a).
494 H.J. FINK ETAL. [CH. 6, $ 5

supercooling, showing that the defects limiting superheating and supercooling

were not necessarily the same and that the limitation of superheating by
defects was far more severe than that of supercooling. In tin, however, there
was a far stronger correlation between the directions of greatest superheating
and greatest supercooling (Feder and McLachlan 1969). The directions giving

I I I I
1

0.08
-*
.- .-.-.-.-.
.9

.95.
,980
. . :. . .-.-4
0.06
O0 900 1800

Fig. 25. K& and K,, as a function of magnetic field direction and temperature for a 16 pm
indium sphere. After Feder and McLachlan (1969).

the highest superheating and the lowest supercooling fields were used in the
) K,,(T), which are plotted against T/T,. Such a plot
calculation of K , ~ ( Tand
is shown for a 18.6 pm In sphere in fig. 26. The apparent increase in K,,,(T)
and ic,,(T) close to T, was due to the fact that t ( T ) = A(T)/Kbecame com-
parable with r and a size effect set in. Size effects such as this have been
observed in all single spheres (which have diameters between about 10 and
CH. 6,B 51 SMALL SUPERCONDUCTORS IN UAGNETIC FIELD 495

50 pm) and powders (ranging in mean diameter from 1 to 50 pm, though

usually sorted into particular size ranges) studied. These size effects make it
almost impossible to get a good extrapolation to rcSh and K,, for samples
smaller than 10 pm, while for the larger spheres (40-50pm) size effects are

e., ---'
71
C

I 0 349 -
I
0
e

--
c

0
0
0

lo O 0
0.155 1
I
0
*.

J l . l . l .
I
1 I I
0.061
I
0.5 0 6 0.7 0.8 0.9 1.0
T/TC

Fig. 26. Supercooling data, given as K,, ( t ) . The temperature dependence near T, is weak
which indicates 'ideal' supercooling close to T,. Notice size effects near T, starting around
= 0.99.The GL parameter K is determined by extrapolation to t = 1. For pure In x,,,,
given by eq. (5.3). is also shown. After Parr (1976b).

barely visible on the scale shown. In practice the 'best' spheres are usually in
the 20 pm range which represents a compromise between large size effects and
the probability of getting a sphere relatively free of defects. This probability
is proportional to r 2 for surface defects and to r 3 for bulk defects.
496 H J . FINK ET AL. [CH. 6, $ 5

However, if the correct choice is made for T, and if the region where size
effects occur is neglected, it is found that K,h(T) and K,,(T)extrapolate to the
same value of K at the transition temperature. In order to get this coincidence
of K,h(T) and K,,(T)for gallium, Parr and Feder (1973) found it necessary to
use eq. (5.9, but when eq. (5.5) was used for tin and indium (Parr 1957,1976b)
the resulting K values were virtually no different from those found using
eq. (5.3). In table 5 are shown the values of K obtained from supercooling

Table 5
Values of the GL parameter K for various elements and alloys obtained from supercooling
experiments

A1 Cd Ga, Gaa Ga, Hg In Pb Sn Zn

0.015‘ 0.012b ~ 0 . 0 8 2 ~~ 0 . 1 3 ~21.66’ 0.115’ 0.062r 0.240b 0.0926O 0.015”
O.14ld 0.137‘ 0.060” 0.087‘
0.061” 0.061’
In InBi0.19% InBi0.395% InBi0.60%
0.061” 0.155” 0.2w 0,349”
0.141” 0.217” 0.302”

Ode la Cruz et al. (1971b). ”de la Cruz et al. (1971a). ‘Feder et al. (1966b). dParr and
Feder (1973). ‘Burger et al. (1967). ‘Smith et al. (1970). gFeder and McLachlan (1969).
”Parr (1976b). ‘Pam (1975).
The measurements (c) should be regarded as preliminary. GaB and Ga, are crystallo-
graphic modifications of the usual orthorhombic a phase. Typical accuracy for the better
experimentsis 1.0% to 2.0%. The second result for the alloys is obtained from the Goodman
equation.

experiments for various elements using both powder and single sphere results.
Also shown are the results for a series of In Bi single spheres. The increase in K
with increasing bismuth content or resistivity for the In Bi alloys (Parr 1976b)
is in reasonable agreement with the Goodman (1961) formula,

where K, is the value of K for the pure element, y is the electronic specific heat
coefficient and p is the resistivity of the alloy. In most cases the same or a very
similar value of K is obtained by extrapolating K J T ) to T = T,.
The values of K obtained from the transitions of thin films in transverse
magnetic field have always been found to be higher than those shown in table
5. Cody and Miller (1972) have shown that, at least in the case of Sn and Pb,
CH. 6 , # 51 SMALL SUPERCONDUCTORS IN MAGNETIC FIELD 497

the KSh(T)values obtained from these and supercooling experiments differ by a

constant factor (2.53 for Sn and 1.33 for Pb) over a considerable temperature
range. They also show that this factor increases steadily from Pb to Sn to In
to Al, i.e., with the degree to which the electrodynamics are expected to be
non-local. Their conclusion is that H J T ) (or HC3(T))is independent of the
non-locality of the electrodynamics, whereas the transitions in perpendicular
field (H,(T) or H,,(T) are sensitive to it. We feel that, pending further theo-
retical investigation of this discrepancy, the K,, results are to be preferred as
they are independent of the type of electrodynamics and are supported by the
K,h results.
As can be seen from fig. 26 the value for K extrapolated from the KJT)
values for the In Bi alloys is unambiguous, and it should be noted that the
temperature range over which K,,(T) is relatively temperature independent
increases with alloying. This is to be expected as the temperature range over
which the GL theory is valid increases with K. The temperature dependence of
K,, stems from the temperature dependence of HC2/H,= z / z ~ , ( T where
) the
parameter K~ increases with decreasing temperature (Gorkov 1959c), and the
temperature dependence of the ratio Hc3/H,2, which also increases with
decreasing temperature (Luders 1967). An increase in K,,(T) with decreasing
temperature is thus expected and is always observed experimentally. However,
as the increase is more rapid than expected, because the enhanced nucleation
at defects at lower temperatures gives an apparent increase in K (Feder and
McLachlan 1969), an exact comparison with theoretical predictions is not
worthwhile.
The K,,, formulae given earlier hold only in the local limit, i.e., close to
T, where (1 - t ) < K’ and A(T) > to.In the extreme non-local limit 1 % 1 --t
9 K’, the non-local superheating field is (Smith et al. 1970)

where C = 1.36. Smith et al. (1970) have shown that the (l-t)-1/12 tem-
perature dependence does indeed hold for their superheating results using tin
and indium powders in the temperature range t = 0.8 to nearly 1, but that the
constant C required to fit these results is N 0.9 and not 1.36. This may be
somewhat fortuitous as the rotation diagrams (fig. 25) show that for super-
heating there is considerable nucleation at defects for t < 0.9. In practice this
equation has not yet been used to find K,h for any element.
As shown in fig. 26, K , ~ ( T
for
) indium has an anomalously large temperature
dependence even when compared with K,,(T).Similar effects are observed for
498 H.J. FINK ETAL. [CH. 6,§5

Sn. For the strong coupling superconductors Hg and Pb (Burger et al. 1966;
Smith et al. 1970)the anomalous temperature dependence of HSh/Hcor K s h ( T )
found for Sn and In is not observed. Indeed, for Hg and to a lesser extent for
Pb, ic,h(T) and K,,(T)are in reasonable agreement for temperatures well below
T,, showing that the region where non-local electrodynamics is applicable is
much wider in these materials than in Sn or In.
As is to be expected, the superheating results of Parr (1976b) show that the
effect of non-local electrodynamics decreases rapidly with alloying. Indeed,
H,,/H, or K,h(T) for the most concentrated alloy (In Bi 0.60%) is almost tem-
perature independent over the range t = 0.85 to 1. Parr (1976b) found that
if the eqs. (5.2) or (5.3) are used to calculate K , h ( T ) and hence K by extra-
polation, the result for the most concentrated alloy is about 30% below the
value found from the supercooling results. However, good agreement,
especially in the case of the alloys, is found between the K(T,)values if eq.
(2.92) is used to calculate K,h(T). This is to be expected as eqs. (5.2) and (5.3)
are only true for K < 1.
The supercooling field for a superconductor plated with a high conductivity
metal is reduced due to the complete or partial suppression of the surface
sheath; the lowest possible supercooling field being the bulk nucleation field

H,, = d / 2 ~ H , . (1.5)

Feder and McLachlan (1969) found that single gold-plated indium spheres
supercooled to the bulk nucleation field near T,. Figure 27 is typical of the
results they obtained using eq. (1.5) to obtain K : ~ . The supercooling field is
lower than in the unplated case especially near T,. The superheating and
supercooling properties were found to change with time when the plated
spheres were left at room temperature. This was probably a result of inter-
diffusion of the gold and indium changing the boundary conditions. Therefore,
the spheres were stored in liquid nitrogen and aged at room temperature.
Small spheres were found to have a lower T, when coated, as did large spheres
when sufficientlyaged. Size effects were also larger in coated than in uncoated
spheres, which is not surprising, as the order parameter is drastically lowered
at the surface of a coated superconductor.
In fig. 27 one finds by extrapolation that K:(T,) = 0.0685 after 1: h of
ageing and that K%(T,)= 0.0620 after both 6 and 20 h of ageing. For lower
temperatures the surface superconductivityis not completely suppressed since
F2(0) is larger at lower temperatures and the result of using eq. (1.5) is that
rcL(T) > K,,(T)for T < T,. Smith and Cardona (1967a) have found similar
CH. 6 , i 5 ) SMALL SUPERCONDUrnORS IN MAGNETIC FIELD 499

results for copper coated powder samples but as their transitions are more
smeared out, their results are more ambiguous and difficult to interpret. The
results for JC:~,calculated from eq. (5.3), are not fully understood, and as their
interpretation depends heavily on proximity theory, they will not be discussed
here.
Although small spheres have in general proved to be the best samples in
which to observe superheating and supercooling in pseudobulk materials, the

A 35pm indium sphere

I I I I I I 1
0.4 0.5 0.6 0.7 0.8 0.9 1 .o
T/Tc
Fig. 27. K:, and K : ~plotted as a function of reduced temperature for a 65 pm gold-plated
indium sphere aged 1.75, 6 and 20 h at room temperature after plating. T. = 3.404 K. The
dotted line shows for a 35 pm indium sphere for comparison.After Feder and McLachlan
(1969).

single spheres studied to date have not been sufficiently small or the powders
sufficiently homogeneous to study the LCP and the second order region. The
sharp increases in KSh(T)andrcs,(T)observed close to T,are, however, evidence
for size effects. Parr (1976b) has plotted some of his results for single spheres
as in fig. 1 and they do indeed show the predicted increase in H,,IH, and
decrease in H,,/H, as r/A(T)decreases. On the other hand, an array of films
(fig. l), indium microcylinders and single whiskers (assumed to be circular
in cross section), have been studied over a wide range of d/A(T) and u/A(T).
500 H.J. FINK ET AL. [CH.6,g 5

As an example the type of critical field diagram obtained for whiskers in

axial magnetic fields is given in fig. 28. The second order region is not as clearly
shown as it is for the films in fig. I , but the superheating field does show a
very decided minimum at about the value predicted for cylinders in recent
calculations by Esfandiari (1976). Neither whiskers nor films showed good
superheatingproperties for large a/A (say a/A > lo), in spite of the fact that

2.6 -

2.0 -

1.5-

1.0 -

0.5 -

I 1 I I I I I I I I I I
2 3 I, 5 6 1 0 9 1 0 20
alh
Fig. 28. The normalized superheating fields H J H . (0) and the normalized supercooling
field HJH, (0)are plotted as a function of a/rl(T)= a[l -(T/Tc)4]1'2/A(0) for tin whisker
no. 2 of McLachlan (1972). H2p/Hc(.) in an axial magnetic field. The theoretical results are
those of Esfandiari (1976). In order to get the fit between experiment and theory shown
above the transition temperature of the whisker has to be taken as 3.692 K and A(0) as
4.85 x lom6cm, in moderate agreement with the results for the whisker shown in fig. 5.

in the case of the whiskers an inhomogeneous magnetic field was used to

inhibit nucleation at the ends of the whiskers.
A study of size effects in indium cylinders was made by Michael and
McLachlan (1974). They discovered that their K,, values were larger than
those obtained for bulk specimens unless a size correction for the value of
H,,/H,, or H,,/H,, was made using the theoretical calculations of Saint-James
(1965) shown in fig. 14. When this was done excellent agreement with the bulk
CH. 6 , § 51 SMALL SUPERCONDUCTORS IN MAGNETIC FIELD so1

value of xsC(Tc)= 0.062 was obtained for a cylinder with a diameter of 7.6 pm.
There appears to be an overcorrectionfor smaller cylinders (2.6-4 pm) as the
K~,(T,)value was found to be less than the accepted value. (There is no
theoretical reason or other experimental evidence for lower K,, values in
very small samples.)
Not only do the results of Saint-James (1965) predict a size dependent
Hc,/Hc, but they predict quantum oscillations in H,, . These oscillations
h -
0.12-

0.10-

-
0.06.

0.04-

2 4 6 8 10 12 14 16 18
"sc

Fig. 29. Shows the quantum oscillations in the supercooling field (ITc3) predicted by
Saint-James (1965) and shown in fig, 14. On the lower X axis is plotted the supercooling
field, on the upper X axis Saint-James normalized supercooling field h. To correspond to
Saint-James' Y axis ( a 2 / t 2 ( t ) ) 1, --t which has the same temperature as a2/C2(r)close to T,
is plotted. The points marked are obtained using the inhomogeneous field technique
(see !j3); those marked 0 are obtained from a uniform field. The two dashedlines show the
region where, from the measurement of the radius a, the change in quantum number n from
zero to one is expected to occur. After Michael and McLachlan (1974).

have been observed by Michael and McLachlan (1974), as is shown in fig. 29,
where the superheating field is plotted against (1 - r). (1 - t ) is plotted on the
Y axis as it is the temperature dependence of Saint-James(1965) Y axis, which
is n 2 / t 2 ( t ) ,close to T, . The first oscillation (n = 0) can clearly be seen and the
second (n = 1) just discerned, and further oscillations are lost in the scatter of
the data points. The dashed lines show the region within which, due to the
experimental error in the measurement of the radius, the transition from n = 0
502 H.J. FINK ETAL. [CH. 6,§5

to n = 1 is expected to occur. Here n is the number of flux quanta enclosed by

the surface sheath at the moment of nucleation. Not only is this an interesting
observation of macroscopic quantum effects but it also provides further proof
that superconductivity in the bulk nucleates from the surface. Similar oscilla-
tions, but in the resistivity, have been observed in indium and indium alloy
cylinders by Shablo and Dmitrenko (1970).

5.3. INTERMEDIATE IC VALUES AND THE METASTABLE SURFACE SHEATH

Detailed analysis of the one dimensional GL equations has shown that the
superconducting surface sheath can exist on a metastable sample below the
bulk critical field (Feder 1967; Park 1967). The limiting field for this state in
decreasing fields, HsEh,has been calculated as a function of ic and it has been
predicted that Hssh< Hc3 for 0.407 c ic < 0.595 with Hssh= Hc3 for
ic = 0.407 and Hssh = H , at ic = 0.595 (Park 1967). The ratio Hssh/Hc is
predicted to vary from 0.976 to 1 as K increases from 0.407 to 0.595. The value
of K = 0.407 for H,, = Hsshwas confirmed by the calculations of Christiansen
and Smith (1968). Effects similar to those predicted above have been seen in
bulk single crystals of Pb and Ta by McEvoy et al. (1967, 1969), and in Pb and
Sn In powders by Smith and Cardona (1967b). As the theory is for a semi-
infinite plane we have chosen to present the results of McEvoy et al. (1969) on
a bulk tantalum cylinder, as a bulk cylinder is an excellent approximation to
a semi-infinite plane if r % ( ( T ) and I(T). These results are shown in fig. 30
where Hssh/H,and H,,/Hc are plotted versus T. Also K is shown, as obtained
from K = 0.417 Hc,/H,. In order to obtain the results for H,,,/H, ancillary
coils had to be placed around the ends of the cylinder to prevent nucleation
there. It can be seen that these results are in qualitative agreement with
the predictions of Park (1967); however, Ifssh= Hc3 at K = 0.39 and Hsshis
not even rapidly approaching H, for ic = 0.48.
Smith and Cardona (1967b) found I f s s h = H,, at ic = 0.39 and 0.396 for Pb
and Sn In (1.99 atx) respectively, and an extrapolation of their results gives
Hslh = H, for K of the order of 0.707. From this one may be tempted to con-
clude that Hssh< H, as long as the material is type I (H, > Hc2).However,
as these measurements were made on spheres and well below T, ,the situation
at the moment is anything but clear.
Smith et al. (1970) have observed that the superheating fields of Sn In
powders tend to be higher than predicted by the GL theory in the K range 0.4
to 0.5. Preliminary measurements by Pettersen and Parr (1976) on a 18.9 pm
In Bi (1.24 at %) sphere give K 1: 0.65 at t = 1 from measurements of H,, . In
CH. 6 , g 5 SMALL SUPERCONDUCTORS IN MAGNETIC FIELD 503

the same sample ‘ideal’ superheating is observed with a ratio &/H, at t = 1

of about 1.6 & 0.1, which is higher than predicted by GL theory. Both these
results indicate a trend for the measured values of Hsh/Hcto be higher than
predicted by the GL theory, at least in this range of K. There are no specific
experimental studies of size effects in this K range.
1 I 1 40.50

\ 0 Hs,/Hc with auxillary field

0 0
0.LO

1.35

1 I I

3.0 3.5 L.0

TEMPERATURE K

Fig. 30. H,,/H, (0)and H.,/H, (0)are shown as a function of temperature for an
electropolished single-crystalcylinder of tantalum. HC3is the field where the surface sheath
nucleates and H.. is the field where superconductivity in the bulk nucleates from the surface
sheath. The Y axis on the right in conjunction with the straight line shows the temperature
dependence of K for this specimen. Note that for K 5 0.39, HC3= H, while for 0.39
< K .c 0.48 the value of H,, ,or H,,hin this case, is lower than H.. After McEvoy et al. (1969).

5.4. LOW K TYPE 11 SUPERCONDUCTORS AND THE OBSERVATION OF INDIVIDUAL

FLUXOIDS

From fig. 2 it can be seen that a superheating field exists and is greater than
H, even for some type I1 superconductors. At first many workers thought that
the formula Hth= H , / K ~ ’ ~[eq.
~ ~ (1.2)]
’ * must hold for all K because it gives
504 H.J. FINK ET AL. [CH. 6 , $ 5

Hsh= H, for K = 0.707, which means that no superheating would be possible

for higher values of K as the surface energy is negative. The phenomenon of
superheating in type I1 superconductors was first discussed by Bean and
Livingston (1964) in terms of a surface energy barrier delaying the entry of the
first fluxoid(s) above H,, . They were unable to give an exact value for Hshbut
thought it to be of the order of H,. Delayed entry of flux was then observed by
two groups (Joseph and Tomasch 1964; De Blois and De Sorbo 1964), using
samples where K > 0.707. The observed barrier field was found to be close to
the thermodynamicfield.
Later GL calculations (see !j 2.3), not subject to the earlier restriction that
K < 1, resulted in the superheating curves such as those shown in figs. 2 and
1 1. These calculations also showed that superheating was basically the same
physical phenomenon in types I and I1 materials and that Hsh> H, even for
low K type I1 superconductors. As discussed in !j 2.3 and shown in fig. 2 for
K > 1.1 there are two superheating fields; these are an upper mathematical
field and a lower field &,where the mathematical solution becomes unstable
(see fig. 2). Because the theoretical and experimental situation for K > 1.1 is
at the moment unclear it will not be further discussed here.
Renard and Richer (1967) were the first to observe superheating above H , in
a sample of pure niobium but as they do not specify their K value, exact com-
parison with theory is impossible. Delayed entry of flux into type I1 micro-
cylinders was also seen by Boato et al. (1965) and their results were in quali-
tative agreement with a calculation by Bobel and Ratto (1965). An interesting
feature of these results was the observation of tiny blips on their oscilloscope
curves correspondingto the entry and exit of single fluxoids.
McLachlan (1970b) observed the entry of single fluxoids at a field of Hsh/Hc
= 1.23 which could be identified with the superheating field given in 3 2.3
and fig. 2 for a sample with a K value of approximately 1.1. Figure 31 shows
some of the results of McLachlan (1970a, b) for an In Bi (1.84 at %) micro-
cylinder (K N 1.l) in a parallel field. Here the off-balance signal of the micro-
susceptibilityapparatus,described in § 3 is plotted as a functionof the magnetic
field Ha for various reduced temperatures. Close to the transition temperature
(fig. 31a) where a < d?A(T) [eq. (2.29)], the transition was reversible.
Some of the observed minima correspond to the entry and exit of single flux
quanta. The points at which the fluxoids enter and leave are in reasonable
agreement with the theoretical predictions of Saint-James (1965), fig. 14 and
Dalmasso and Pagiola (1965). The transitions in a perpendicular field were
also reversible (second order) in the same temperature range as those in
a parallel field, in agreement with the GL theory.
CH . 6 , $51 SMALL SUPERCONDUCTORS IN MAGNETIC FIELD 505

Below the LCP, as expected, the transition became irreversible. From fig.
31b it is seen that the diamagnetic susceptibility originally decreased as the
increasing field caused an increase in the penetration depth. At the point
marked H, = Hshthe first fluxoid entered and the diamagnetic susceptibility
increased. This process was observed for the next four fluxoids but the sixth

-1 0
I

5
I
10
I
15
I
20

“m-
-I
a
m
LL
LL
0
I

11nV t z.932
Hc3

0 25 50 75 100 125 150

EslZ!=
. 5 HCI 1 nV t z.932

0 25 H (gauss)
50 75

Fig. 31. The off-balance signal from the detection system is plotted as a function of the
magnetic field for a low K type I1 superconductor at various fixed temperatures.A description
of the various phenomena observed is given in the text. Data from McLachlan (1970a, b).

fluxoid was unpinned and driven in and out of the sample by the alternating
field, giving rise to a differential paramagnetic effect. This interpretation is
supported by the fact that when the alternating magnetic field was reduced by
a factor of ten, only the eighth fluxoid was unpinned and gave rise to a dif-
ferential paramagnetic effect. When the field was reversed the susceptibility
506 H.J. FINK ET AL. [CH. 6, J 5

curve was completely different with a change in slope marked by the value
of Hc3and a return to the original diamagnetic line marked by H,, .
At still lower temperatures (fig. 31c) individual flux quanta could not be
observed, but a small increase in the diamagnetism marked the irreversible
entry of the first fluxoids or the superheating field H, = Hsh.There then
appeared to be a surface sheath which made the sample appear diamagnetic
until the field labelled HBin the diagram was reached (the surface sheath may
be related to the ‘giant vortex’ postulated by Fink and Presson (1968)). At this
point the differential susceptibility became paramagnetic as expected for a
type I1 superconductor between H,, and H,, (or IT,,). In decreasing the field
from above H,, changes in the slope of the susceptibility curve mark H,, and
Hc2 while H,, is identified as before. Further hysteresis loops given by
McLachlan (1970a’ 1970b)show in more detail how the major hysteresis loops
depended on temperature and also show the entry and exit of individual
fluxoids in minor hysteresis loops. Also shown in fig. 31d is a hysteresis loop
in a transverse field.
When the values of H,, and H, = Hsh in transverse fields were multiplied by
2, to take into account the demagnetization coefficient, it was found that the
values obtained agreed with H,, and Hsh,found for parallel fields, within the
experimental error. Using values of H, obtained from the results of Kinsel et
al. (1964), McLachlan (1970b) showed &/H, = 1.23 for a/A > 20 in agree-
ment with the results of § 2.3 and fig. 2 for a superconductor with a K of s 1.l.
The expected IC value for In Bi (1.82 at %) is about 1.1 and a similar IC value
was also derived from measurements of t ( T )and A(T)in the latter reference.
The values of H,, derived from the lattter work were, however, lower than
expected for the bulk material, thus indicating supercooling. Another some-
what surprising and unexplained result was the observation of a minimum in
H,h/Hc as a/A(T) decreased towards the LCP, which, although predicted and
observed for type I superconductors, is not predicted for a material with a
K value of this magnitude (see fig. 7).

5.5. MEASUREMENT
OF 6 (T, H )

Recently, Parr (1975, 1976a) has made measurements of A(T,O) over a wide
range of temperatures and of 6 (T,H) for temperatures just below T, in
magnetic fields approaching Hsh on Sn,In and In Bi single spheres. The values
of A(T,O) were obtained by observing the change in the off-balance signal
S(T,O)at the H,, field, where His relatively small, as a function of temperature.
The normalized temperature dependence of this signal ( P a r 1975) is
CH.6,g 51 SMALL SUPERCONDUCTORS IN MAGNETIC FIELD 507

S(T, 0)
-=
+
1- 31(0)y/r 3(1(0)y/r)’
S(0,O) 1 - 31(0)/r+ 3(A(O)/r)’ ’
which if y is known enables A(O)/r and hence A(0) to be determined from the
data. It was found that the temperature dependence of 1 in all cases was
equally well described by I(T) = 1(O)y, where y = 1/(1-t4)”’, or 1(T) =
IBcS(O)ZBcs,where Z,, is the BCS temperature dependence. The values of
1(0) found in this way agreed with other experimental values for A(0) found
from the temperature variation of A@).
To determine 6(T,H)for a fixed temperature, the change in the off balance
signal between the superconducting and normal state was measured as a
function of field. As the variation was small the measurements had to be
repeated and averages taken. Because of the demagnetizing field, the total
field varied over the surface of the superconducting sphere and the data
therefore contains information about an averaged penetration depth d(T,H).
A procedure was developed for extracting the bulk field dependence of 6(T,H)
from the data (Parr 1975). It was found that the field dependence of 6 came
close to being a universal function of H/H,,.At &,y 6(TyH,,)/1(T,0)N 4 2
in agreement with eq. (2.49) and d6/dH diverged as shown in fig. 10, while at
low magnetic fields 6(T,H)/1(t)N 1+a(H/H,,)z, which is all in good agree-
ment with predictions made using the GL theory.

5.6. STUDY OF METASTABLE PHASES OF ELEMENTS AND ALLOYS

The possibility exists that metastable phases of elements or alloys may form in
small spheres due to rapid quenching or other factors and these phases may
remain quenched-indue to the lack of a nucleation site for the crystallographic
phase transition. So far, this phenomenon has only been observed and in-
vestigated in gallium. In the original work by Feder et al. (1966b), gallium
after being sonicated in ethyl alcohol saturated with sodium oleate, was
quenched into liquid nitrogen after (i) being cooled to room temperature,
(ii) being quenched to 0°C and stored for 24 h. The first sample was found
to contain Gas and Ga, in the ratio 5:l while the second contained Ga, and
Gas in the ratio 4: 1 plus a trace of Ga,. From an examination of their powder
type hysteresis loops Feder et al. (1966b) were able to conclude that:
(i) For Ga,, K,, = 0.085 and qh= 0.082 at 0.94 K (T, was not measured but
is known to be 1.082 K).
+
(ii) For Gas, T, = 6.20 0.10 K and also K,, = 0.13 and K,h = 0.19 at
4.2 K.
508 H.J. FINK ET AL. [CH.6, I 5

+
(iii) For Ga,, T, = 7.62 0.10 K and Ga, is probably a type I1 supercon-
ductor with a K of about 1.66 fairly near T, .
When Parr and Feder (1973) studied carefully selected single spheres, which
had been slowly cooled and frozen in a stream of cold nitrogen gas, it was
found that virtually all the spheres were in the p phase. When held just below
room temperature for extended periods only a few of the larger spheres with
obvious defects made the transition into the stable a phase.
Extensive measurements on fl phase single spheres enabled the following
parameters to be measured: T, = 6.07 0.03 K, H,(O) = 538 L- 5 G, K,, =
0.141 & 0.002, and A(0) = 880 f 100 A. From the shape of the H,(T) curve
it was deduced that p gallium is a weak superconductor, as is a gallium. There
are some errors in the interpretation in the original paper due to a faulty
calibration of the germanium thermometer. This was corrected for by Parr
(1974) who studied the isotope effect in p gallium and found that for 69Ga,
T, = 6.10 L- 0.02 K and for "Ga, T, = 6.02 & 0.02 K which yields an a
of 0.43 f 0.02 in the equation T, M-'.
N

5.7. TRANSITION
AND NUCLEATION TIMES

Early work by Faber (1957) showed that the transition time in bulk super-
conductors of the metastable superheated superconductingstate to the normal
state was limited by eddy current damping. Valette and Waysand (1975) have
recently performed experiments where the flux pulse due to the transition of
single (10-40 pm) Hg spheres is led along a transmission line into a special low
noise amplifier and the integrated pulse signal of the amplifier output is fed
into an oscilloscope provided with a switchable storage screen. The pulse
shapes showed that the transition times of particles of even this small size are
limited by eddy current damping. The nucleating process could not be
observed directly as it is shorter than the 6 nsec dead time of the amplifier.
Combining their own and previous results, Valette and Waysand (1975) con-
cluded that eddy current dampingwas probablythe limiting factor in observing
the nucleation process, even for a region as small as approximately T(T)in
diameter. At this point the transition time would be N 4 x lo-" sec which
must be taken as a provisional upper limit for the nucleation time.

5.8. APPLICATIONS
One possible application of superheating is the detection of charged nuclear
particles using a superheated powder.
 CH.6,§51 SMALL SUPERCONDUCTORS IN MAGNETIC FIELD 509

A moderately small superconductor in a field H such that H, < H < Hsh

can jump into the normal state under the influence of an external perturbation.
Therefore, when a superheated superconducting powder is traversed by a
particle beam the resulting destruction of superconductivity can be moni-
tored, using the methods already described, as a function of the number of
incident particles. Experiments by Valette (1971) showed that the condition
for a superheated granule to be driven into the normal state is that the energy
loss in the granule be sufficient to raise the temperature of the granule by an
amount

Experiments have been done using 8- irradiation emitted from radioactive

7 9 A ~9 81amalgamated in the Hg spheres of the superconducting powder
(Bernas et al. 1967), and using a van de G r d electron beam (Rosenblatt
et al. 1973).
Experiments have also been done using high energy 0.5-7 GeV electrons
from an electron synchrotron (Druiker et al. 1975). Here the destruction of
superconductivityis not primarily due to the high energy electrons themselves
but rather to the photoelectrons created by the transition radiation which is
due to the relativistic electrons crossing the dielectric (paraffin wax) to metal
(Hg) interfaces. The latter application in particular shows some promising
results.
As small superconducting grains are bistable they can naturally be used as
computer elements. However, as even 40 pm Hg spheres have switching times
of the order of 400nsec they would not be very fast.

5.9. RECENT EXPERIMENTAL DEVELOPMENTS

Very recently, Yogi (1977) has made a study of superheating in In, Sn and the
In Bi and Sn In alloy systems in a rf magnetic field. In this method the sample,
a sphere of approx 1-2 mm in diameter, was placed in a helical resonator at
the point where the magnetic field was a maximum and the Q of the resonator
was monitored as a function of the peak rf field. A noticeable change in the
Q-value of the resonator marked the superconducting to normal transition,
and the peak rf field at this transition could be determined to within an
accuracy of & 10%. Whilst considerable superheating was observed in the
rf magnetic fields, the same samples showed very little superheating in a
quasi static magnetic field.
510 H.J. FINK ET AL.

For In and Sn the observed superheating fields at t N 1 were very similar

to those which had been found earlier by Feder and McLachlan (1969) and
Smith et al. (1970). At lower temperatures, H,h/Hc was found to vary as
1/(1 - t ) l I 6 which is characteristic of line nucleation (Yogi 1970). Therefore it
was inferred that the nucleation centres for the normal phase were in the form
of a line in the above experiments. Whether this temperature dependence is
characteristic of transitions in a rf magnetic field is not yet known, as this type
of nucleation may well be caused by inhomogeneities at the surface, such as
grain boundaries. The latter are not present in single crystal microspheres
whosevalues of HSh/Hcwere found to vary as 1/( 1 - t)‘” by Smith et al. (1970),
which is characteristic of plane nucleation.
For the alloys whose K values were as large as 1.75, the results were con-
sistent with the theoretical predictions for K < 1.1 discussed in $ 2 and shown
in fig. 2. Unfortunately, the few experimental results for K greater than 1.1 are
such that it is impossible to decide if the upper limit of the superheating field
is determined by the solutions to the GL equations in $2.3 or the theoretically
smaller field due to instabilities determined by Fink and Presson (1969).
However, Yogi’s (1977) results and those of McLachlan (1970b) are in dis-
agreement with Kramer’s (1968) theoretical predictions for the fluctuation-
limited superheating field.

Acknowledgements

The authors would like to thank H. Parr for makinga number of his papers
available to us prior to publication.
One of the authors (H.J.F.) would like to thank M.R. Esfandiari and R.S.
Poulsen for their assistance with the numerical solutions and permission
to use their unpublished results.
Another of the authors (B.R.B.) would like to thank the PEL Library,
DSIR, Lower Hutt, New Zealand for making library facilities available to her.
We all thank Professor F.R.N. Nabarro for his interest in this work and his
constructive criticism.
The manuscript was typed at the opposite ends of the globe by the following
people: Miss Susie Butz, Miss Tamara Gibbons, Miss Aelise HOUX, Mrs.
Nora Main and Mrs. Gwen Murphy, while most of the figures were drawn by
Mrs. Katherine Peach; the authors would like to acknowledge their debt to all
of them.
 SMALL SUPERCONDUCTORS IN MAGNETIC FIELD 511

Appendix - Derivation of equation (2.57)

Starting with eq. (2.21) and substituting for Fou = X , the first derivative of
g is

Assuming that a is known, g = 0 and dg/dX = 0 are two equations with two
unknowns whose solutions for Xand Ho 3 HT(X)are

With B 3 Z2(X) Zo(X)/Zf (A’) eq. (A.2) transforms into

X2(3B- 1) = 2U2(2B- 1). (A.4)

Expanding B in a series for X 2 < 1 and neglecting powers of X ” and higher,

eq. (A.4) becomes

1 -a2/3+ 1 1X2/32+7X4/15360 = 0. (A.5)

A solution ofeq. (A.5) near the LCP where (1 -u2/3) 4 1 is

(a)’ = Fi =~ ( 1 - ~ 2 ) [ 1 - ~ ( l - ~ ) ] .

Equation (A.6) reduces to eq. (2.42) when the higher order term (1 -3/u’)’ is
neglected. Substituting eq. (2.42) into eq. (A.3) and neglecting higher order
terms in (1 - 3/a’) leads to

Near the LCP a’ N 3 so that the term in brackets [ J is 3 for u2 = 3. With

this substitution eq. (A.7) becomes eq. (2.57) in conventional units.
512 H.J. FINK ET AL.

List of symbols
vector potential magnetic field at Landau
coefficient of free energy (2.22), Critical Point (LCP), conven-
(2.23) tional units
radius of cylinder magnetic field corresponding to
coefficient of free energy (2.22), the lower limit of the meta-
(2.24) stable surface sheath
specific heat; coefficient of free thermodynamic critical field
energy (2.22), (2.25) applied field normalized by
LCP = HolHL
velocity of light; coefficient of
superheating field normalized
free energy (2.93), (2.94)
by LCP
thickness of film supercooling field normalized
superconducting electron pair by LCP
charge = 2e thermodynamic critical field
modulus of GL normalized normalized by LCP
order parameter, r dependent second order phase transition
(2.6) field normalized by LCP
modulus of G L normalized current density
order parameter, independent Fourier component
of r mean free path
Gibbs free energy of normal mass of superconducting
state electron pair = 2m(m = free
Gibbs free energy of super- electron)
conducting state magnetization
normalized Gibbs free energy coefficient
difference (2.5) coefficient = 4, for super-
applied magnetic field, conven- heating field
tional units coefficient = 1613, for thermo-
bulk thermodynamic critical dynamic critical field
field (2.35) electron density of states at the
lower critical field for flux entry Fermi surface for one spin
into bulk superconductor conduction electron density
bulk nucleation field (1 5 ) pressure
surface nucleation field (1.4) superfluid velocity
applied field at some value 0, coordinate (cylindrical); radius
conventional units; G L nor- of sphere
resistance; surface resistance
malized applied field = H./d\/z
signal from detection apparatus
x Hc temperature, ambient
local magnetic field on equato- transition temperature
rial plane of a superconducting temperature of LCP
sphere
TIT.
superheating field conventional
units; superheating field, GL TLITc
volume; BCS electron phonon
normalized = H , h / d i H, interaction constant
supercooling field, conventional volume of sample which ex-
units; supercooling field, GL cludes magnetic field
normalized = H.& H, GLnormalized volume = V/A3
 SMALL SUPERCONDUCTORS IN MAGNETIC FIELD 513

Fermi velocity P . C temperature dependent super-

coordinate cooling K, value for coated
temperature dependence of the superconductors derived from
penetration depth eq.(1.5)
thermal expansion coefficient 4 I I temperature dependent super-
coefficient heating K, value defined by eq.
electronic specific heat coeffi- (5.2)
cient; coefficient (2.42). K9h temperature dependent super-
one-half of the Bardeen- heating K, value derived from
Cooper-Schrieffer energy gap eqs. (5.2), (5.3)
m
(Tc-T)/(T,-Td = ( I - t ) / 4n) = C (X+I)-";n = 2, 3,
k=O
...
(1 - f L )
field and/or mean free path A, A(T),A ( f ) low field penetration depth
dependent penetration depth (2.7)s(2.36)
LL W'L)
first variation of GLnormalized
Gibbs free energy difference
t, W),C(r) coherence length (2.9)
1. 0.18fmp/kTo, BCS (Pippard)
second variation of GL norma- coherence length, fiuF/wA(0)
lized Gibbs free energy differ- I
I 3.1416
ence 01 stress Ith component
third variation of GL norma- phase of order parameter, r
lized Gibbs free energy differ- @(r) dependent
ence I coordinate, cylindrical
fourth variation of GL norrna- X function of I(2.4)
lized Gibbs free energy differ- P resistivity
ence Wr) complex order parameter, r
strain, ith component dependent
IW absolute value of order para-
zeta function of 3 = 1.202 mter
(Riemann) lYml absolute value of order para-
GL K value = 1(T)/ C(T) meter in zero field, independent
temperature dependent super- of r
cooling K, value defined by eq. Jl(r) modulus of complex order para-
(5.1) meter, r dependent

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 CHAPTER 7

PROPERTIES OF THE A-15 COMPOUNDS

AND ONE-DIMENSIONALITY
BY

L.P. GORKOV
The Landau Institutefor TheoreticalPhysics,
Academy of Sciences of the USSR, Moscow, USSR

Progress in Low Temperature Physics, Volume VIIB

Edlted by D.F. Brewer
0 North-HollandPublishing Company, 1978
Contents

1. Short survey of the properties of the A-15 compounds. Some basic theoretical
ideas 519
2. The choice of the electronic term for the linear chain. Instability of the
spectrum 529
3. Interactions. Connection between structural and superconductive fluctuations in
the linear chain. The role of the ‘three-dimensional effects’ 533
4. Peculiarities of the three-dimensional electron spectrum in the A-15 lattice due to
the interchain tunnelling. Fine structure of the density of states 544
5. Structure properties of the A-15 compounds in the simplest model. Phonon
spectrum 552
6. Some results concerning the superconductivity of A-15 compounds 568
7. Discussion 579
8. Summary. Some concluding remarks 584
References 588
1. Short survey of the propertiesof the A-15compounds. Some basic
theoretical ideas

Since the discovery in 1954 of the high T, for V3Si(T, = 17.0 K) and
Nb3Sh (T, = 18.2K) materials with the A-15 structure were intensively
investigated. Such interest, continuing for more than twenty years, was
connected partially with the importance of their practical applications for
high field magnets. However, the real reason for the numerous, very difficult
experimental studies was the hope of achieving still higher temperatures for
superconductivity. In fact, the highest critical temperatures up to date have
been obtained in Nb,Ge (T,N 22.2 K) which again is a member of the
A-15 structure family. There are still no ‘room’ (nitrogen) temperature
superconductors. Meanwhile as a result of these efforts a new and interesting
physical field has appeared. This review paper will be devoted to this latter
side of research in the A-15 type materials which is of general physical
interest. The problem of obtaining high T, superconductors will not be
discussed.
From the very beginning it should be emphasized that the character of
the experimental results in this field, their accuracy and the unambiguity of
the interpretation are still very far from the level which is achieved now in
the physics of ordinary metals. The cause lies in the numerous difficulties
of a metallurgical and technological character concerning the preparation of
perfect samples. Despite these complications the main features of the
phenomena are now well established. A few excellent reviews (Testardi 1973;
Weger and Goldberg 1973; Izumov and Kurmaev 1974) exist to which I
shall refer the reader in the cases when details are needed. Nevertheless
it seems desirable to summarize briefly the basic experimental facts to define
the problem which is discussed theoretically in the main part of the paper.
Among the first unexpected results were the observations of the anomalous
temperature dependence of the magnetic susceptibility and the Knight shift
in the A-15 compounds. (The latter is usually proportional to the magnetic
susceptibility.) It is well known that for the ordinary metals both these
quantities are almost independent of temperature. The diamagnetic part of
the susceptibility is connected, as a rule, with inner electronic shells of the
520 L.P. GOR'KOV [CH. 7,$ 1

atoms. As for the paramagnetic contribution, it is commonly ascribed to the

Pauli spin susceptibility of the conduction electrons and can be expressed
in terms of the electronic density of states, v(E):

x = pB!v(&)ch- '(&/2T)ds/4T.

-
Due to the large energy scale (the Fermi level EF 5-10eV) of electron
bands in metals, V ( E ) changes slowly (v(E) w v(0);E = E-E,). The order of
magnitude of v(0) varies from the value v(0) 0.3 states/eV.atom (for two
N

spin directions) for non-transition metals to v(0) 2-5 states/eV -atom

N

for the typical transition metals. There are several simple qualitative explana-
tions of the enlargement of v(0) for transition metals based either on the
relative narrowness of the d-electron bands for these elements or on the role
of the Coulomb interactions.
A striking peculiarity in the behaviour of the susceptibility of the A-15
compounds is its remarkable temperature variation, extending over the
whole room temperature interval. This can be seen from fig. 1 which repro-
duces the recent data on the susceptibilityof V3Si. The change of the magnetic
susceptibility with temperature reaches about 30% of its value which, in
turn, is rather large in these compounds.
The specific heat at low temperatures is usually divided into a sum of
electronic and lattice vibration contributions

c = aT+bT3, (1)

T(K)
Fig. 1 . Plot of the temperature dependence of the magnetic susceptibility, ,y, for V3Si
(Maita and Bucker 1972).
CH. 7,811 PROPERTIES OF A-15 COMPOUNDS 521

where the electronic part, linear in T, can again be expressed in terms of

v(0):

a = *x’v(O). (2)

(The values of v(0) estimated from the magnitude of the magnetic suscepti-
bility and from the specific heat measurements, differ from each other.)
The temperature dependence of the magnetic susceptibility and rather
large values of v(0) [eqs. (I), (2)] have been considered together by Clogston
and Jacarino (1961) in the phenomenological ‘density of states peak‘ model
for conducting electrons. Of great importance is the fact that the width of the
peak in the electronic density of states at the Fermi surface introduced to
fit the observed temperature dependences has to be of the order of a few
hundred Kelvins (Clogston and Jacarino 1961). Meanwhile a rough estimate
of the d-electron band width AE based on photoemission data gives for
V,Si AE % 3.4 eV. (See Testardi 1973 and Weger and Goldberg 1973 for
more details.)
The most important feature of the A-15 compounds is the phenomenon of
the low-temperature structural transformation observed for Nb,Sn and
V,Si (the Batterman-Barrett ‘martensitic’ transformation). This transition
from the cubic to the tetragonal phase occurs at T, N 43-50 K for Nb,Sn
and T, N 20-25 K for V,Si. In figs. 2 and 3 the results of X-ray studies of
the lattice parameters are given for Nb,Sn (Mailfert et al. 1967) and V,Si
(Batterman and Barrett 1966). According to the symmetry theory analysis
(Anderson and Blount 1965) this transformation is expected to be a phase
transition of the first kind. This question will be essential below. Figures
2 and 3 show that the correspondingdiscontinuities of the lattice parameters
are in any case not well pronounced for V,Si. (For discussion of this ques-
tion see Testardi 1973.) No hysteresis effects have been observedwithcertainty.
The nature of the structural transformation became clear after the ultra-
sonic velocity measurements for V3Si had been performed by Testardi’s
group (see Testardi 1973). They studied the temperature behaviour of the
elastic moduli and observed for the elastic shear modulus C, = +(C,, - C12)
a remarkable temperature softening (at cooling) down to zero values at
T = T,. A similar behaviour was later found for Nb,Sn (Rehwald et al.
1972). On fig. 4 the shear moduli C, for Nb,Sn and V3Si are plotted as a
function of In T.
It seems that the Batterman-Barrett transformation should be accepted as
the basic property of these materials. From this point of view the anomalous
522 L.P. GOR'KOV [CH. 7,g 1

5.300 --- I---

Nb,Sn

L
al
..../

al
V
.r
4.J,
c
-

0
1 8 . I
20
I I I I
40
I
I, I I I
60
I I I

80
I , ---_ % 0
T(K)
Fig. 2. X-ray data for the temperature dependence of the lattice parameters in Nb,Sn
(Mailfert et al. 1967).

4.728
c/a = 1.0022
C

4.724

\
4.720 I
I
I Cubic
I n
I
Tetragonal
4.716
i
phase
I p-u4a
*Bil
I T"a20.5 K

4.712 I I I I I

8 12 16 20 24 6
T(K)
Fig. 3. X-ray data for the temperature dependence of the lattice parameters in VISi
(Batterman and Barrett 1966).
CH.7.0 1J PROPERTIES OF A-15 COMPOUNDS 523

temperature dependences of the magnetic susceptibility and elastic modulus,

responsible for the transformation mentioned above can be considered as a
‘precursor’ behaviour above the temperature of the structural transition.
Rather close critical values for the structural and superconductive tran-
sition temperatures for Nb,Sn and V,Si immediately put forward the
question of whether both phenomena are connected. There are numerous
pieces of evidence in favour of this suggestion. For instance, both T, and
T,,, are strongly dependent on deformation and composition; T, depends
on whether the cubic-tetragonal transformation in the given sample occurs,
or not. The ‘saturation’ of the growing tetragonal deformation at Toin the
V3Si is easily seen on the corresponding curve in fig. 3 [‘arrest of the struc-
tural instability’, according to the terminology of Testardi (1973)l.

I I I I I I I

25 50 75 100 150 200 250 300

T(K)
Fig. 4. The temperature dependence of the elastic shear modulus, C., in VsSi (Testardi
1973) and Nb,Sn (Rehwald et al. 1972) plotted as a function of lnT.

However, the question is whether this interdependence between both

phenomena results from the occasional closeness of the critical temperatures
(the same characteristic energies) for both transitions or whether both of
them are a consequence of some intrinsic physical mechanism. Perhaps the
most important and strange experimental fact which forces us to consider
this last point of view, is the softening of the phonon frequencies in Nb,Sn
and V,Si discovered in the inelastic neutron scattering experiments (Shirane
et al. 1971; Axe and Shirane 1973). The striking feature of the results is
that the softening (at cooling) of the phonon frequency concerns phonons
with large wave vectors, of the order of the reciprocal lattice vector. These
data (Axe and Shirane 1973) for Nb,Sn are shown in fig. 5.
524 L.P. GOR’KOV [CH.7,# 1

Very often the suggestion is discussed whether high Tc’s in these com-
pounds are due to some hypothetical mechanism of ‘enhancement of super-
conductivity by lattice instability’. As for the existence of this enhancement,
the point of view accepted below would give a negative answer.

14 -
- -0-T-295 K
--e-T=120 K
12 - *T= 62K
*T= 46K
10 -

8-
w
Q
E -
h
0-
b
3 6-

4-

I
0. 0
Fig. 5. Dependence of the dispersion law for the transverse mode (q = (Zs/a)[C, C, 01,
ell [lTO]) on temperature, according to the neutron inelastic data in Nb3Sn (Axe and
Shirane 1973).

In what follows we shall try to answer the question whether it is possible

to unite the main physical facts within the framework of a certain theoretical
idea. Therefore many of the experimental results, mentioned above, will be
discussed again in more detail in connection with their theoretical inter-
pretation.
CH. 7,8 11 PROPERTIES OF A-15 COMPOUNDS 525

At first sight the crystal structure of the A-15 materials looks rather
complicated. The unit cell for the chemical composition A,B is shown in
fig. 6a and contains two ‘molecules’. Non-transition atoms B occupy the
body centered cubic (b.c.c.) positions. The transition element atoms A are
situated on the faces of the cube. The space group of the cubic structure is
Of (Pm’n) and contains non-trivial translations. In fig. 6b some details of
the tetragonal phase are shown, namely, that the tetragonal distortion is
accompanied by the sublattice displacements of transition atoms. The space
group for this phase is DZ,,[see Testardi (1973) for more details].

Fig. 6. (a) Crystal structure of the A-15 lattice compounds, A3B. Circles correspond to
non-transitionatoms in the b.c.c. positions. Crosses are used for transition element atoms.
The dashed line is to emphasize the idea of the three orthogonal sets of linear transition
atoms chains. (b) The displacement of sub-latticesof the transition atoms in the tetragonal
phase is shown by arrows.

The dashed lines in fig. 6a for the cubic phase are to demonstrate the
geometrical image of the A-atoms, lying along the three different sets of the
orthogonal linear chains. The importance of this picture was first emphasized
by Weger (1964), who pointed out that due to the small overlap between
d-orbitals of the transition atoms from different chains, d-electrons of the
single chain in the first approximation move only along the chain’s direction.
We will discuss the reasons for such a suggestion later. At present we mention
only that this observation is the underlying idea for all the current theoretical
models, including the model to the discussion of which the main part of
the present paper is devoted. In this section it is reasonable to give also a
short survey of the two main previous theories of the A-15 compounds
properties and their starting microscopic suggestions concerning the elec-
tronic energy spectrum.
526 L.P. GOR’KOV [CH. 7,9 1

The first one was the Labbe-Friedel-Barisic (LFB) model. (See Testardi
(1973) and Weger and Goldberg (1973) for references.) They have suggested
for Nb,Sn and V3Si wide and strongly overlapping s-p electron bands with a
large number of current carriers, as is commonly assumed for the transition
metals. At the same time they claimed that some of the d-electron bands are
almost empty but their bottoms* are very close to the position of the Fermi
level in the s-p bands, p. If the d-electrons of the chain were one-dimensional,
the density of states, v(E),near the edge of the band, c 0 , had to be of the form:

It seems almost evident that this singularity would be located at the point
r ( k = 0) of reciprocal space. However, other possibilities for the location
of the Van Hove type singularities (3) exist, and they are enumerated in
Weger and Goldberg (1973).
When introducing this suggestion about the position of the Fermi level,
the peak in the density of states accepted in the article by Clogston and
Jacarino (1961) on a phenomenological basis, can be connected with the
square root singularity (3). The angular momentum degeneracy of the
d-electron levels in the atom is partially lifted by the lattice field. Hence,
different d-sub-bands can be taken. We prefer not to go into all the details
of the LFB model, limiting ourselves to qualitative ideas only.
The contribution of the d-electrons to the energy of the crystal (at T = 0)
is equal to

(The sum over the index i corresponds to the three different sets of chains.)
This contribution could be very essential for the elastic properties. In fact,
in the presence of deformations the bottom, cOi, of each of the electron bands
shifts in some way (different for each of the three orthogonal sets of chains).
The electronic contribution to the elastic moduli, which are proportional to
the second derivatives of expression (4)with respect to strains, can be made
negative and large enough to provide the instability of the cubic phase, if p
is chosen close enough to the position of the singularity (3). The Batterman-
Barrett transformation is therefore interpreted in this model as a sort of
Jahn-Teller effect -the degeneracy in the electron numbers in different

*Or the tops of the filled d-band.

CH. 7,§11 PROPERTIES OF A-15 COMPOUNDS 527

chains is removed by the redistribution of electrons between chains accom-

panied by spontaneous distortion. In the case of a singularity (3) at the point
r of the reciprocal lattice symmetry considerations give the softening of the
shear modulus C,.
To summarize, the LFB model with a suitable choice of parameters gives
a reasonable account of most of the A-15 material’s structural properties.
Its vulnerable points are the following (a) the one-dimensionality manifesting
itself in eq. (3) for the density of states; (b) the necessity to choose the Fermi
level very close (-20 K) to the edge of the d-band.
Let us discuss both these difficulties. A very crude (in the tight binding

-
approach) estimation of the values for transfer integrals, B, between different
sets of chains gives the order of magnitude, By a few tenths eV. It should
be mentioned that the packing of the transition element atoms in the A-15
structure is usually even denser than in the corresponding metals. At the
same time the tunnelling could be even more intricate due to the presence
of the large s-p shells of the non-transition atoms. However, in any case
one should expect that the three-dimensional corrections to the one-
dimensional electron spectrum are too large to take literally the one-dimen-
sional Van Hove singularity (3).
An attempt to improve the Labbe-Friedel picture in this particular point
was the so-called ‘RCA model’ (see Testardi 1973; Weger and Goldberg
1973). The idea was essentially the same; the bottoms of the d-electron
bands are close to the Fermi level position of the s-p electrons. However,
even with the three-dimensional corrections, the density of states for the
d-bands, v&), should be larger than that for the s-p band (the assumed
narrowness of the d-band). Therefore in the RCA model one considers
again three sets of chains with steplike densities of states:

(a 9 1, the edges of d-zones, E O i ,

are strain dependent). As in the LFB model
case, the appropriate parameters can again be chosen to fit most of the
experimental data in a rather satisfactory way. The distance of the Fermi
level from the edge of the d-band is now about 100 K.
Therefore one sees that in any case the second objection against the LFB
model also concerns the RCA model. It seems difficult to point out any
reasons why at the overlapping of the very wide (- 10 eV) s-p electron
528 L.P.GOR’KOV [CH. 7,g 1

bands with the d-band, the bottom of the latter has to be so close to the Fermi
level. This could simply be an occasional numerical coincidence for Nb,Sn
and V3Si. However there is evidence that some characteristic features of the
best investigated Nb,Sn and V3Si are also inherent in other members of this
class of material (Testardi 1973).
A few words should be said about the attempts to get an answer by the
straightforward computer calculations of the band structure for these rather
complicated compounds (see for results Weger and Goldberg 1973 and
Matheiss 1975). Starting from first principles, one has to pass through about
20 bands before the position of the Fermi level is reached. (The latter is
defined by the whole number of electrons on the A and B atoms per unit cell.)
Different authors estimate the accuracy of their calculations in different ways.
We believe it would be very optimistic to state that the relative positions of
bands are now defined better than within the limits of a few eV. The large
difference between the results of Weger and Goldberg (1973) and Matheiss
(1975) confirms this suspicion. The main objection against this ‘first principle
approach’ consists in the neglect of many essential features of the Fermi
liquid theory, i.e. interactions and scattering effects. Therefore we believe
that the question of the band structure cannot be resolved now in a straight-
forward way and is open for phenomenological suggestions.
In concluding this section let us formulate the starting points for the follow-
ing consideration. The most important suggestion we will accept (Gor’kov
1973, 1974), is that there exist some d-bands which do not overlap
with the s-p electron valence bands. More exactly, it is enough for the latter
to be completely occupied. In the real crystal the wave functions of the
d-electrons are strongly different from the d-functions of the free atoms.
Designating for the sake of simplicity the corresponding zones as d-electron
ones we at the same time emphasize their origin from the transition atoms
in the chains. However, it is supposed that these bands are formed self-
consistently, with all the lattice field and interaction effects taken into account.
In our picture the d-electrons are the only carriers in the system.
In the next section we consider these electrons in the first approximation
as one-dimensional, taking only their motion along the chain into account.
The interchain transfer will be considered as a perturbation; it is responsible
for many details of the physical results.
It is supposed below that the reader is familiar with the basic ideas and
results of the theory of phase transitions and the BCS theory of super-
conductivity. Therefore many references which have already become ‘classic’
will be omitted.
CH.7,#21 PROPERTIES OF A-15 COMPOUNDS 529

2. The choice of the electronic term for the linear chain. Instability of the
spectrum

The simplified theory of metals and dielectrics connects the conduction

properties with the number of electrons per unit cell. Substances with an
odd number of electrons have half-filled energy bands and have to be metals.
If the band is filled up to the top, the corresponding electrons do not con-
tribute to conductivity. Hence, metals with an even number of electrons per
unit cell exist only if there is an overlap between some bands. This picture is
widely known. However it is worth emphasizing that the physical con-
sequences are independent of the initial band model. One of the main results
obtained in the framework of the Fermi liquid theory consists in the proof of
the correctness of this concept even in the presence of interactions between
electrons. The famous Luttinger theorem argues that the whole number of
states per unit cell (for two spin directions)inside the volume in the reciprocal
unit cell limited by all Fermi surfaces, always corresponds to an odd or even
integer.
For a single chain of transition atoms there are two A-atoms in the unit
cell, i.e. an even number of electrons. Therefore one should understand
whether it is possible to reconcile the concept of the non-overlapping bands
with the experimental evidence of a large number of carriers in the A-15
compounds.
We have mentioned that the assumed electron band comes from d-electrons
moving in the crystal field of the surrounding atoms. Therefore let us investi-
gate in more detail what sort of limitations on the zone structure arise due to
the special symmetry group of the A-15lattice. In fig. 7 the crosses represent
the transition atoms in the chain, the circles for the B-atoms reflect the
symmetry of the field of the host lattice matrix. The point group is D4,,,
however the full space group contains non-trivial translations (the screw
axis). The group of symmetry for the single chain coincides with the small
group of the wave vector at the point X of the simple cubic Brillouin zone
(fig. 8). The corresponding representations {XI, X,, X , , X4} for electron
wave functionsat the point Xwere known (Gorzkowski 1963). All representa-
tions are twofold degenerate.
To get the electron energy spectrum near the zone boundary (near the
point X)it is necessary to expand the product of representations X:.X, on
the representations of the point group D,,,,. This is a standard group theory
approach for the selection of all the non-zero matrix elements between the
wave functions of the representation X i . Only X , ,X4will be needed.
530 L.P. GOR'KOV [CH. 7,$ 2

The distribution of the matrix elements for some combinations of physical

parameters over representations A: ,A , , B:, B i of the group D4,, =
D4xCi (which are the only ones to appear in the products X , * - X , and

Fig. 7. Symmetry of the crystal field for an electron moving along the chain direction.

Fig. 8. The simple cubic Brillouin zone.

X,'.X4), are listed in table 1. For twofold degenerate representations it is

convenient to write down the electron Hamiltonian near the point X in the
matrix form using the Pauli matrixes 8,, 8,, 8,:
CH.7,821 PROPERTIES OF A-15 COMPOUNDS 531

Table 1
The distribution of the matrix elements of the strain
tensor components, elk,the sublattice displacements,
u l , momenta and the magnetic field, H, over some
representations of the group Da.

The factors A , and B, contain, in principle, all combinations from table 1

with their own coefficients. First we note that the componentsp x ,p y (for the
chain along the [Ool] direction) can appear only in the presence of three-
dimensional effects and should be omitted. All spin-&pendent terms, other
than (u-H ) , are proportional to the spin-orbital interaction constant. At
least for Nb,Sn and V,Si the latter is small and can be neglected. Therefore
one sees from eq. (6) that in the absence of strains, &ik and sublattice dis-
tortion, u,, the electron term (6) corresponds to the following two branches
of the spectrum:

e = f ul"1; (6, = n/a-p.). 0

Therefore the energy band as a whole for a single chain has the structure
shown in fig. 9. For an even number of electrons from the two transition
atoms (6 in V,Si and 10 in Nb3Sn) a band arises filled as shown in fig. 9.
In other words the position of the Fermi level (Fermi surface) is fixed auto-
matically at the point X. The finite slope for both branches, &/*, = fu,
provides the metallic properties of these compounds, The other two repre-
sentations XI, X , have deldp, = 0 at the point X and will not be considered
further.*
In the presence of the distortions e l k and u, eq. (6) is of the form:

*These representations could give a base for the LabbbFriedel singularity (3) in tho
density of states.
532 L.P. GOR'KOV [CH.7,8 2

The deformation potentials d, and d3 do not remove the two-fold degeneracy

(7). Actually, as will be discussed below, these terms are responsible for the
temperature variation of the bulk modulus. The latter varies very slowly.
Therefore both d, and d3 can be neglected in comparison with dl We will .
also omit yu, in (6') for simplicity in all the expressions.
Now it is seen that in the presence of strains the energy spectrum (7)
splits into two branches:

Fig. 9. Electronic band supposed for terms X2,X., at the point X.The lower branch is
occupied. The shadowed region corresponds to other filled bands (s-p bands).

with the gap A, = dl(&,,-&yy). Calculating in the usual way the electronic
contribution to the free energy of the crystal

(where the s u m is taken over three sets of chains and two branches (8), and
the potential 60, is given for unit volume), one can easily obtain for its
elastic part (
CH.7,831 PROPERTIES OF A-15 COMPOUNDS 533

Logarithmic integration over the interval T/v Q IS,] n/a has appeared
in eq. (10). Introducing the elastic modulus C,,as usual

we get the logarithmic temperature-dependent contributions to the moduli

C,,and C,,:

SC,, = -(2d$naZu) In (AEIT); SC,, = +(d:/zazv) In (AEIT),

(12)

where AE - v/a is of the order of the band width. For the shear modulus

SC, = -(3d,2/na2v) In (AEIT). (13)

Equation (13) corresponds to the softening of the C,at cooling. The meaning
of these results becomes clear from a closer look at expression (8) for the
split spectrum. The deformation now results in the appearance of a gap in
the energy spectrum of fig. 9. Therefore the energy of the whole system
decreases at deformation. Similar considerations were first exploited by
Peierls in his famous proof of the instability of the periodic one-dimensional
array of metallic atoms with respect to the alternating of its period. In our
case the symmetry of the A-15 lattice reduces this instability to the instability
with respect to acoustic shear waves (and/or the sublattice optical phonon
mode at k = 0, if the term yu, is included).

3. Interactions. Connection between structural and superconductive fluctuations

in the linear chain. The role of the ‘three-dimensionaleffects’

The results obtained above are incomplete in two respects. The obvious one
is that electrons are not one-dimensional. However, for the time being the
discussion of the three-dimensional effects will be postponed. One has to
recognize first that the problem of the Peierls structural instability in itself
is more complicated than it looks in the light of the arguments of the pre-
ceding section. Historically this fact was first discovered in the theory of
‘one-dimensional metals’ (Bychkov et al. 1966; Dzyaloshinskyi and Larkin
1971). One can verify that a one-to-one correspondence exists between the
problem mentioned and that for the A-15 compounds. Qualitatively one can
understand this fact noting that the band structure in fig. 9 looks like the
534 L.P. GOR’KOV [CH. 7,s 3

band structure for a chain with the period a* = -)a reduced to one-half of
the corresponding Brillouin zone.
In this section we have no intention of going into all the details of the
mathematical side of the problem. However it would be desirable to explain
its most prominent features to get a deeper insight into the consequences.
The physical reasons why some doubts are relevant concerning the Peierls-
like arguments given above, become clearer with a more attentive look at
eqs. (8) and (13). According to eq. (13), for any arbitrary weak interaction dl
there is a temperature, Tp, at which the electronic contribution cancels the
‘bare’ lattice part of the elastic modulus, C:’).The developing spontaneous
distortion leads to a gap in the energy spectrum (8). However, from the naive
point of view it seems possible, at least in principle, to reduce the whole
energy of the system due to superconductivity (i.e. if the energy gap in the
eq. (8) is of ‘superconductive’ origin). Indeed, both phenomena arise due to
the electron-phonon interaction and both consist in the enhancement of
roughly the same weak electron-phonon coupling constant by a logarithmic
factor which becomes large at low temperatures. The difference between the
Cooper effect and the Peierls instability lies in the cut-off value 63 entering
into this enhancing factor ln(iS/T). For the Cooper effect 6 is of the order
of some averaged phonon frequency (-0.01 eV). The cut-off AE in eq. (13)
is supposed to be about several eV. Therefore with weak interactions one
could expect for T,(T,J values much larger than T,. Meanwhile, these two
temperatures are rather close to each other both for Nb,Sn and V3Si and
are m a l l enough for us to believe that the interaction is still a weak one.
For many of the A-15 compounds the structural transformation has never
been observed. Certainly one could point out many reasons explaining the
absence of this latter (three-dimensionalcorrections, for instance). However,
we shall investigate the question in more detail.
For a moment let us forget about phonons and consider only short-range
and weak electron-electron interactions. In our model there are a number of
interaction constants, g,, corresponding to different electron scattering
processes between electrons from ( 2 )bands (7). They all are shown in fig. 10.
Let us just state without proof, that according to the results (Bychkov et al.
1966; Dzyaloshinskyi and Larkin 1971) the physical peculiarities of the one-
dimensional system are defined mainly by g,. Therefore in the following
qualitative discussion only this scattering constant will be mentioned.
The first step would consist in an attempt to get some first order corrections
to the scattering processes of fig. 10. There are two contributions represented
by the diagrams in fig, 11. If we omit the numerical coefficients these matrix
CH. 7,s 31 PROPERTIES OF A-15 COMPOUNDS 535

...
Fig. 10. Possible interactions between electrons describing different scattering processes
between the branches (+) of the zone on fig. 9 near the point X = n/a.

elements can be written down using Green’s functions (Abrikosov et a]. 1965)

where + ( p ) are the two electron branches (7) and w, = (2n+ 1)aT. For the
diagram (a) of fig. 11 one has

Fig. 11. The 6rst order perturbation corrections to the scattering amplitude g1 of fig. 10:
(a) Cooper-type channel, (b) Peierls-type, or the charge density wave channel.

and

for the diagram (b).

In (a) and (b) we used the fact that both points f a / u at the zone boundary
differ by the vector of the reciprocal lattice K = 2a/a and are equivalent.
536 L.P. GOR'KOV [CH. 7,$3

Hence, the integration over 6 can be extended over the interval ( - n/a, ./a).
The frequency sum gives the well-known relation:

Substituting it into expressions (a) and (b) one finds out that both of them
are proportional to

s d6
S
US
k g: -th - = k 2g: In -
2T
6
T

(here we have introduced a certain cut-off value, 5, for the range of

integration).
The magnitude of g , for both corrections is enhanced by a factor ln(G/T),
which at low enough temperatures can compensate the weakness of inter-
action g , + 1 :

Therefore to get the correct expression for the scattering amplitude between
electrons (i-) in the temperature range (16), one should sum all the correc-
tions of the form g,[g, ln(6/T)]". Keeping this in mind, we have to investigate
which class of diagrams gives contributions of this order of magnitude.
In the three-dimensional BCS theory of superconductivity one collects all
the ladder diagrams (a). As a result, the familiar expression for the corre-
sponding 'scattering amplitude' - the vertex part r - is of the form:

This pole which exists at attraction g , < 0, defines the onset of super-
conductivity i.e., the transition temperature T, .
The scattering channel (a) of fig. 1 1 ought to be called the Cooper-type
channel. Diagram (b) corresponds to the dielectric electron-hole pairing,
i.e. to charge density waves (CDW). This channel can be called the Peierls-
type channel. (Note the different signs in expression (15) for (a) and (b).)
Therefore the important question is whether any competition between the
two channels could exist in the subsequent corrections to the vertex part.
CH. 7,G 31 PROPERTIES OF A-15 COMPOUNDS 537

Straightforward calculation of the diagram shown in fig. 12 immediately

gives the corrections

which at the temperatures defined by eq. (16), has exactly the same order of
magnitude as the second approximation for the ladder Cooper-type diagrams.
The necessity to include the corrections from one type of channel into the
diagrams for the other, even with weak interactions, leads to a rather com-
plicated set of equations usually named ‘parquet’ equations. It is useful to

Fig. 12. Insertion of the Peierls-type channel contribution into the Cooper-type diagram.

consider their structure in more detail; however, we will postpone this to the
end of the section and start with the discussion of the physical consequences
obtained. The striking difference between the ladder approximation and the
more exact approach becomes evident if one compares the corresponding
results for the possibility of the Peierls-type pairing. In the ladder approxi-
mation for the Peierls channel one would get the pole-type behaviour (17)
of the vertex r for the repulsive sign of g, (the opposite sign in (15) if com-
pared with Cooper pairing). The ‘parquet’ calculations reproduce expression
(17), which has no pole at g, > 0. Therefore the metallic state is stable for
repulsive interactions between electrons. If g, < 0, the same pole (17)
appears simultaneously in both parts of the vertex r responsible for the BCS
and CDW types of pairing. In other words, with weak attractive electron-
electron interaction the instabilities with respect to the structural and super-
conducting transformations correspond to identical critical temperatures,
Torit.It should be mentioned that in reality there are no phase transitions in
the one-dimensionalcase and this statement means only that the fluctuations
corresponding to both types of ordering, develop simultaneously beginning
with this characteristic temperature, Tcrit.As far as only the electron-
538 L.P.GOR’KOV [CH. 7,j 3

electron interactions are considered, any instability means the instability of

the electron subsystem. In our case this instability is characterized by two
electronic order parameters.
Let us now consider how these resuIts will be altered if phonons are
ncluded (interaction with the lattice). In addition to the short-range vertexes
g, of fig. 10, phonon-induced scattering processes are now possible, which
are the result of an exchange of virtual phonons between electrons. The
corresponding scattering amplitude is proportional to

where w1 - w 3 and p 1 - p 3 are the corresponding changes of the frequency

and momentum of the upper electron in fig. 10. We have written the inter-
action (18) in a completely schematic form. Actually the corresponding
D-function reflects the symmetry properties of the active phonon mode
(gephis connected either with acoustic modes (being proportional to dl , d2),
or with the optic ones, y, etc.). The frequency Q is of the order of a typical
frequency of the phonon mode w,(q). The latter generally speaking, has a
three-dimensional behaviour since the d-electrons are not the only source of
elastic forces in the lattice.

-
The important feature of the interaction (18) consists in the retardation
effects. At low temperatures w1 - w3 T < coo, SZ and this effect can be
neglected. In this case eq. (18) reduces to the usual attractive interaction of
the BCS theory. In the opposite limiting case (at T % wo) the interaction (18)
is small (- (f2/T)’). If only the electrons of one chain are considered,
expression (18), in general, has to be averaged over the qL, i.e. over the
dependence of w,(q) on q1 along the flat (one-dimensional) Fermi surface.
The electron-phonon interaction changes the phonon D-function. The
corresponding Dyson equation:

contains the self-energy part for phonons, n (the polarization operator).

Its meaning, if eq. (19) is rewritten in the form:

D-’(q) = W(q)-n(q).>, (19’)

consists in the renormalization of the phonon frequency. If we neglect all
other corrections, the first approximation for n has the form of the bubble
CH. 7,831 PROPERTIES OF A-15 COMPOUNDS 539

shown in fig. 13a. As a matter of fact, in the end of the previous section we
have calculated the corresponding contribution of fig. 13a into Z7 for the
acoustic modes. It was found to be proportional to ln(dE/T). Hence, one can
interpret the results (12), (13) as a renormalization of the elastic moduli due
to the first-order electronic corrections. The dimensionless electron-phonon
coupling constant in the case of a shear wave is equal to
= 3d:/aazvCio).
geph
2

(+I

0<:D- (-1
(a)
(-1
(b)
Fig. 13. Schematic representation of the polarization operator: (a) The first order
electroniccontribution, (b) General form of the polarization operator. Trianglescorrespond
to the electron-phonon vertices improved by various corrections.

The first approximation of fig. 13a should be, in principle, improved by the
electron-electron and electron-phonon interactions. This is schematically
shown by triangles in fig. 13b, which represents the change of the electron-
phonon interaction due to electronic corrections. The effective electron-
phonon interaction is determined by many details of the real system.
The essential point is that if T B w o , SZ, one can neglect in the expression
for n(q)any insertion of internal phonon D-lines. Therefore let us determine
the temperature T p ,at which the renormalized frequency w,,,(q, T ) in (19')
tends to zero:

If Tp found as the solution of eq. (20) is large, Tp p wo, all the calculations
above are self-consistent and the Peierls instability (or the giant Kohn
anomaly) occurs in our system.*

*As it was mentioned, wo(q) has well pronounced threedimensional features, therefore
the temperature Tp could be. the temperature of a real three-dimensional structure
transformation.We will come back to this point a little later.
540 L.P. GOR’KOV [CH.7,g 3

However it could turn out that the ‘bare’ electron-phonon constant

g.bhis small enough and, as a result, the solution T, of eq. (20), is such that
+
Tp coo, 8. This case needs an additional investigation. At T 4 wo the

-
phonon induced electron4ectron interaction (18) reduces to the short-
range BCS attraction -gZphand for the one-dimensional system has to be
included into the whole scheme described above. As far as phonons are
supposed to be the only source of attractive interaction, the critical tem-
perature, Tcri,,if it exists, is smaller than wo. As before, at Tcrltthe system
manifests instability with respect to the coexisting structural and supercon-
ductive fluctuations.
These arguments were based on the one-dimensionalpicture (in particular,
the dispersion oo(q,)has been neglected). The next question concerns the
role of the three-dimensional effects. In the framework of the one-dimensional
theory it was possible to ascribe the fact that the structural transformation
temperature T, is sufficiently low, to the absence of solutions of eq. (20) for
Tp > coo. The three-dimensional electron tunnelling between different
chains could independently reduce T,. In fact, if the electron spectrum is of a
three-dimensional character there is no more exact ‘nesting’ of the Fermi
surfaces which has been the cause for the appearance of the factor ln(dE/T)
in the Peierls channel. If the energy scale for the three-dimensionality is a
certain T*, the temperature dependence of the renormalized frequency
would saturate at T T*.t The general speculations about the role of the
N

three-dimensional effects become clearer if one considers in more detail the

structure of the mathematical equations corresponding to the described
phenomena. No attempts have been undertaken to solve these equations
even numerically owing to the evident reasons of their extremely complicated
structure and the great number of unknown factors. Therefore in what
follows we again use the schematic language of diagrams omitting almost all
details of the crystal structure, the specific form of interactions etc.
For the beginning some convenient form of the exact equations for the
vertex part, r, will be derived. Perhaps, the following comments could
clarify the physical reasons why this quantity is one of the most important
in the theory. Let us, for instance, introduce some external ‘force’, fi,, with
a definite space symmetry acting on the electronic density. The corresponding
Hamiltonian will be of the form ~ , f , , ,where 8, is the Fourier component

?For an array of weakly interacting parallel chains some other possibilities exist for the
exact ‘nesting’ of the slightly curved Fermi surfaces (see, for example, Horovitz et al.
1975). These considerations are not applicable to the three orthogonal sets of chains in the
A-15 compounds.
 CH.7, 8 31 PROPERTIES OF A-15 COMPOUNDS 541

of the electron density operator. The external small perturbation, fi, gives
a linear response for the electronic density (Di,). The latter can be written
as follows:

This relation is shown in fig. 14. The brackets used here for simplicity of
notation mean the usual integrations and summations over the internal
momenta and frequencies (p,p’). One sees therefore that if r contains the
solution of the pole type for some T and some g the response (a,,) can

Fig. 14. Schematic representation of linear response for the electronic density to an
external ‘force’ he.It is Seen that this response could get infinite if the vertex part, r,has
pole behaviour (see text).

become infinite. This fact corresponds to the instability of the electronic

system with respect to an arbitrary small external ‘force’&. At this point
one sees the analogy between the ‘soft vibration mode’ concept for some
lattice distortion and the instability with respect to an electronic order
parameter. In particular it is possible to consider a more generalized form of
the perturbating Hamiltonian, including the ‘Cooper-pairing forces’,
$ + $ + A , , and define the temperature of the onset of superconductivity T,
in the same way.
It is also useful to rewrite eq. (19) in the absence of retardation effects
(T < wo)in the form which is shown diagramatically in fig. 15. One sees
that if the vertex part tends to infinity, the D-function will be infinite, too.

D(q) Db(q) D,(q)

-=-t

Fig. 15. The phonon Green’s function, D, expressed in terms of the ‘bare’ Dco,function
and the electron vertex part. Pole behaviour for r a t some q means softening some active
phonon mode.
542 L.P.GORKOV [CH. 7,I 3

From the point of view of eq. (19’) it means the softening of the renormalized
frequency for one of the phonon modes considered.
Returning to the derivation of the exact equations for r let us introduce,
following Dyatlov et a]. (1957), three blocks: C(p, ,p2;p3,p4), Pl(pl , p 3 ;
p 2 , p4), P2(pl p4;p 2 ,p3) whose definition is seen from fig. 16. Each block
is the sum of all diagrams which are reducible with respect to the division of
the diagram into parts connected only by two G-lines. Therefore the whole
vertex r can be written as the sum:

where R(p, ,p 2 ;p 3 ,p4) denote all the diagrams which are irreducible in the
sense explained above. Several examples for R are shown in fig. 17 beginning
(a) (b)
9 3!

C(.. 1

p4

Fig. 16. The definition of blocks for the Cooper-type (a) and Peierls-type (b) channels.
The dashed lines show the corresponding cross sections giving in the one-dimensional case
the logarithmic enhancement of the interaction constants at low temperatures.

with the ‘bare’ interaction* g. For each of the three blocks there is an evident
relation which is a generalization of the Dyson equations for D- or G-
functions

*The only specificity of the phonon-induced interaction is that it becomes effective in

the narrow range of energies wo < EF very close to the Fermi surface.
 7s. 0 31 PROPERTIES OF A-15 COMPOUNDS 543

K )([R(pI,l ; p i - ~ ,I+K)+C(pI, Z ; P ~ - K , Z+K)

P I ( P I , P I - K ; P ~ , P ~ +=
+P2(Pi I+ K ; 1, Pi - rc)lG(0W+ 4
9

x rb2,I + K ; r, p Z + m . (21 "1

The system of eqs. (21) (21') and (21") is exact and it is needless to say that
it is also correct for the three-dimensional case. For ordinary three-
dimensional metals the approximation of the BCS theory consists in
neglecting (for weak interaction) all diagrams which do not introduce the
logarithmic enhancement factor ln(&/T). Therefore in the BCS theory two
blocks PI,P2 remain small at any temperatures and thus R can be reduced
to the 'bare' interaction constant. The critical temperature is determined as

+HRt
the pole of the vertex part corresponding to the Cooper block and can be

,l-TP3
PL- --P4 t

Fig. 17. A few examples of nonparquet diagrams.

found by solving the homogeneous equation (21') where for r (21) only its
part Cis to be substituted. In principle, similar solutions of the homogeneou-
equation are possible even for the P-block; however, the logarithmic enhances
ment appears in the Peierls-type channel only for the one-dimensional case.
In the parquet approximation which has been mentioned so often before
all the non-trivial diagrams for R (which, as can be shown, do not exceed
g3ln(&/T)) and all the corrections to the Green's functions are omitted.
As for the latter, they give a contribution of the order of g2In(G/T) and can
be taken into account as corrections to the first parquet approximation by
means of the procedure elaborated in Menyhard and S6lyom (1973). For
mathematical details we refer the reader to the original papers (Bychkov
et al. 1966; Dyaloshinskyi and Larkin 1971; and Menyhard and S6lyom
1973).
The main result of the parquet approximation which was stressed all the
time, is that in the one-dimensional case the system of equations for Cooper-
and Peierls-type blocks can not be decoupled. The critical temperature,
TCl,(,of the form
Twit = ( 6 9 dE) lgl"z exp (- l/lsl) (22)
determinesthe starting point for the developmentof both typesof fluctuations
544 L.P. GOR’KOV [CH.7,s4

Now we return to the question how the fluctuation regime becomes a

real phase transition due to effects of three-dimensionality. Among the latter
the interchain electron tunnelling seems to be the most important for the
properties of A-15 compounds. We have already mentioned it as the cause
which destroys the mechanism of the logarithmic enhancement of inter-
actions in the Peierls channel due to cancelling the exact ‘nesting’ of flat
electron and hole Fermi surfaces. However the solution for the homogeneous
part of eq. (21”) for the Peierls block could still exist if the energy scale, T*,
characteristic for ‘three-dimensionality’, is not too large in comparison with
Tcrlt(22). In fact, the integration in eq. (21”) extends over the region of
momenta and frequencies which is not essentially altered by a change of the
electronic spectrum, partly due to the assumption T* < AE, and partly to
the slow logarithmic variation of all inner blocks when the lower cut-off T
is substituted by T*. In other words, the solution of (21”) could exist as a
result of the compensation of the main one-dimensional contributions in
both parts of this equation. As for superconductivity,the origin of the Cooper
factor ln(G/T) is a consequence of time reversal invariance only, and we
believe that if an attraction provides the existence of Tcrit(22) in the frame-
work of the strictly one-dimensional theory, superconductivity always
appears at some T, < Tcritwhen the electron interchain transfer is included.
Among other three-dimensional effects, as was pointed out in Gor’kov
and Dzyaloshinskyi (1974), there are the three-dimensional dependences of
the phonon frequencies on their wave vectors. The same applies to the ‘bare’
constants gi which are of Coulomb origin. The influence of this effect on
the Peierls (structural) pairing is not so drastic. We will not deal with these
problems any further.
The aim of this discussion was to point out a very attractive possible
explanation why T, and T,,, in the A-15’s are not far from each other. The
idea is that both transitions are driven by electronic order parameters. One-
dimensionality as the first approximation is essential in order to shift both
temperatures to rather low values of the order of TCrit < coo. The large
tunnelling could be the factor explaining the absence of the structural
transformation in most of the A-1 5 materials.

4. Peculiarities of the threedimensional electron spectrum in the A-15 lattice

due to the interchain tunnelling. Fine structure of the density of states

Although we have stressed that the electronic band of fig. 9 can be considered
as a general form of solution for the electron moving along the chain in the
CH.7.8 41 PROPERTIES OF A-15 COMPOUNDS 545

crystal field of the A-15 lattice, for the beginning in what follows an even
more simple picture will be chosen. The three-dimensional features of the
electronic spectrum will be considered in the tight-binding approximation
by introducing two transfer integrals: A, for the motion along the chain,
and B, the transfer integral between nearest neighbouring transition atoms
of two orthogonal chains (A % B). Further we will point out which of the
results obtained are sensitive to the tight binding model.
If a:’, af’ are the amplitudes of the electron wave functions for the two
sublattices of the transition atoms of the x-chain, the electronic spectrum is
defined by the equation

where the column {@} is constructed from the three subcolumns

Let us write down only the equation for a:), at). The remaining equations
can be obtained by a cyclic permutation of (x, y, z):

In this approximation we have for the one-dimensional band

when the positioning of the Fermi level is close to the point X,E in eqs. (23),
(23’) is small and the Fermi surfaces are not too far from the corresponding
faces of the simple cubic Brillouin zone. Therefore almost everywhere on the
zone face the three-dimensional corrections for the spectrum of the electrons
on the x-chains can be obtained by substituting into (23’) the perturbation
expressions for a:’, a t ) proportional to ( B / A ) ~ : ; . After some calculation
one gets instead of eq. (7):

~l‘fi= T*(sinz~p,a+sin2~pya-2)
+ -
[ ( O S , ) ~ T * 2(sin2+p,a sin’ fpya)211’z. (25)
546 L.P. GOR’KOV [CH.7,g 4

Here we have introduced

T * = 4B2a/v = 16B2/AE. (25’)

Both solutions for the electronic spectrum (25) have the form of two slightly
shifted and split electron and hole branches and for many phenomena
studied below, it can again be considered as a ‘three-dimensional spectrum’
for each of the three independent sets of chains. In general eqs. (25) are
incorrect at the edges and in the comers of the cubic zone where the
degeneracy in eq. (23) becomes fourfold and sixfold respectively (see below).
It is easy to check the following property of solution (25):

The density of states V ( E ) can be defined for each of the two branches (25).
The number of electrons occupying all possible states with energies lower
than E , N(E),is equal to (per unit volume)

The expressionsfor the numbers of electrons and holes can be easily calculated
as the corresponding volumes restricted by the energy surfaces (25). For
instance, for the electron pockets

In expression (28) E is measured in units of T’(2 = &/TI)and E, K are the

standard notations for the elliptic integrals. The relation (26) results in the
identity

Therefore from eq. (29) one sees that the stoichiometric composition (the
numbers of electrons and holes are equal) corresponds to the position of the
Fermi level at
CH.7, $41 PROPERTIES OF A-15 COMPOUNDS 547

The density of states, v(E), is determined by differentiating eq. (28). Its

electronic contribution is

[-2<I<O.

The density of states V ( E ) = v , ( E ) + Y ~ ( E ) written in this form can be con-

sidered, if one desires, as the sum of contributions from the three pairs of
the reciprocal cube faces, i.e. as the sum over all the three sets of orthogonal
chains. The normalization factor in eq. (31) is chosen to give the density
of states for the one-dimensional chains in the absence of three-dimensional
effects (T* 0). The full density of states v,(&)+vh(&) is symmetric with
respect to the point E = -T* (30).It has two logarithmic singular peaks at
I = 0 and d = -2. Near E = 0, for example, one has:

V(E) = v(0)(2/7c2)In (32T*/lsl). (32)

It is instructive to understand in more detail the origin of these singularities.

Let us consider expression (25) near the edge of the cubic face (at small
6, = n/a-p,). One of the roots (25) looks now as

E(1X) N -2T*(ts,U)z+(v632/[2T* cos2 ($p,a)]. (33)

Denoting 1’ = ~ ( S , U ) ~5’
, = (v6,)2/[2T*cos2(~p,a)]
and introducing hyper-
bolic variables :

r2-1’ = E; (1 = s

) ~ the evaluation of the number

to perform the integration over d j p / ( 2 ~ for
of states, N(E), one immediately obtains the logarithmic singularity (32) in
the density of states. Therefore this singularity arises due to the saddle-like
form (33) of the energy surfaces near the edge of the cube along the whole
length of the latter. The origin of the second singularity at E = -2T* is
the same but it is connected with the lines pa = 0 or pp = 0. (Note the
absence of any small prefactor in eq. (32), which could arise, at first sight,
as the result of three-dimensionality!)
548 L.P. GOR’KOV [CH. 7.8 4

The logarithmic singularity (32) is smoothed by many physical factors

like defects or impurities. Putting this last question aside we discuss in this
section only the limitations connected with the tight binding approach. First
of all, there is no exact equivalence between the lines py = 0 (or pz = 0)
and the edges of the cube even in this approximation. The evident reason
lies in the fact that the edges of the Brillouin zone are the lines of matching
of the energy spectrum for the two orthogonal sets of chains. Therefore near
these lines one should investigate in a more careful way the splitting of the
fourfold degeneracy of energy levels of the unconnected chains. Restricting
ourselves to the case of small 6, = z/u-p,, 6, = n/a-p,, it is possible to
simplify the fourth order determinant in the system of eqs. (23), (23‘) for
( x ) and (y) chains. After simple but rather tedious calculations it is possible
to show that the corresponding solutions have two low-lying branches
(8 4 B) which have to be determined from the equation (Gor’kov and
Dorokhov 1976a):

+6,2)-u463,2
&2[v2(6: +6,2)+4B2~vz~2]+2eB~~v,~2av(s:
+4B41~,12~4(6,4+614)
= 0. (34)

For an arbitrary E T* the fourth term is small and can be omitted. In

N

this case eq. (34) describes the smooth transition of the Fermi surface from
the x-chain zone face to the y-chain face. At small E 4 T* and 6, $- 6,:

2vasB21vz124 4 6 ; +4B41vz12a46,2 = 0,

with the definition (25’) for T* and Ivz12 = 4cos2(#p,u) this equation can
be shown to be identical to eq. (33). The second pair of roots for the equation
given by this fourth-order determinant near the edge of the cubic face, is
of the form:

I
The gaps f4B Icos(+p,a) (far from the corners [l 111) are of the order of
T*’I2. The energy band constructed in this model can be identified as the
o-band in the numerical calculations for V,Ga (Weger and Goldberg 1973).
Comparing the results for the value of splitting at the point M with eq. (36)
* N 300 K. (In Weger and Goldberg (1973) the overlap between
one gets Tvl0,

-
various d-bands was obtained. Nevertheless, we believe that the above
estimate provides a correct order of magnitude for T* a few hundred
Kelvin.)
CH.7,§41 PROPERTIES OF A-15 COMPOUNDS 549

The tight-binding model described above has been introduced, partly, to

get the possibility for comparison of the results with the numerical calcula-
tions (Weger and Goldberg 1973), partly for convenience to deal in what
follows with analytical expressions. However, it should be emphasized that
the only physical approximation of the theory is the assumption that the
transfer integrals for electrons on the orthogonal chains are small in com-
parison with the width of the one-dimensional band. There are no other
physical reasons but simplicity to construct the latter in the way it has been
done above (i.e. using in eq. (23) the transfer integral A between only the
nearest neighbours along the chain). Therefore an important question arise,
whether the results will change essentially if the one-dimensional electron
band is of a more complicated form than the cosine law (24), and in particular
whether the singularity (32) in the density of states exists in the general case.
It appears that the symmetry of the density of states with respect to the
point (30) is destroyed. This is due, first of all, to the annihilation of one of
the logarithmic singularities. In fact, it is easy to verify that the form (33) of
the energy spectrum at the lines p,, = 0 or pz = 0 is a consequence of (24)
only. In the general case one obtains:

wheref, and fi,, are some functions of p z . Hence, the range of the saddle-
like form of the spectrum (33) is limited in pz (by the condition that the left
side has to be small: E < T*).
As to the singular logarithmic peak (32) at E = 0, it always exists, though
the coefficient before it is, in general, numerically different. Indeed, as has
been mentioned, at the edge of the cube the energy levels are fourfold
degenerate in the one-dimensional chain approximation. A more detailed
investigation which we will not carry out here shows that, if the interaction
between neighbouring orthogonal chains is small (B Q d E ) the twofold
degeneracy of the electronic spectrum is still present along the whole edge
of the cube (p, = n/a,p y = ./a).* For the low-lying branches ( E ;5 T* 4 B),
instead of (34), we have a new equation

*The two-fold degenerate term along the whole edge of the cube is a consequence of the
. logarithmicsingularityinthe density of states is due to the special
symmetrygroup O h 3The
relationship between the coefficients in (34’) which is a consequence of the fact that the
fourfold degeneracy of onadimensional chains at the cube edge is broken by the small
overlapping between chains.
0
550 L.P. GOR’KOV [CH. 7,g 4

containing some new functions q1,.’ q2,,. At small E < T * and at appro-
priate signs of q1,=and q z , z it again gives the singularity:

m = v(o)(2/n:z)rIn (T*/l+, (32’)

where

The magnitude of < N1 and the position of this singularity with respect to
the chemical potential, corresponding to the stoichiometric composition (i.e.
pStoich T*) cannot be defined in the general form. According to (28) a
N

change 6p T* corresponds to the stoichiometry of the order of T*/AE

N

(a few percent).
The fine structure of the electron density of states of necessity leads to a
temperature-dependent contribution to the paramagnetic susceptibility

The experimental data for V3Si and Nb3Sn show a remarkable tem-
perature dependence of the magnetic susceptibility. We note a rather
important detail that in the strictly one-dimensional approach the only
(logarithmic) temperature dependent contribution to x comes from the
representation B2- of table 1. However it is proportional to the square
of the interchain transfer integral value (Gor’kov 1973, 1974). Hence, the
temperature dependence of the susceptibility for V3Si and Nb3Sn must be
attributed to some structure of the electronic density of states.
Figure 18 shows the results (Gor’kov and Dorokhov 1976a) of numerical
calculations for the magnetic susceptibility (37) in which the density of
states (31) has been used (at various positions of the Fermi level). It can be
seen that both increase and decrease of x at cooling are possible for the two-
peak structure. As far as we know, the correlation of the temperature
behaviour of the magnetic susceptibility with composition has never been
studied. One can find some data showing that the difference x(T,)-x(300)
changes for samples with different T,. However to the author’s knowledge
-=
there is no data indicating that x(TJ ~(300).Therefore this could be an
CH. 7,8 41 PROPERTIES OF A-15 COMPOUNDS 551

additional argument in favour of the fact that the peak at e = -2T” is

actually smeared out according to the previous discussion.

5%
F 0
‘ 7
t ~
x2.
r 2.3’
n
0 \
‘.---------;/--
-------------
/ / R~ 4 ,//
,--gS~----.
4)
-0.05
-0.20
?-.0.40
0’ -1.00
2.1 - / / /
//
//

,/- /
/
/

1
/
1.9 -*’ /
/

/
/
/
1.7 - /
/
/
--/’
1.5- I I I I I I

If only the peak (32’) at E = 0 survives, as seems most probable, the

temperature dependence x ( T ) for the corresponding position of the Fermi
level is of the form:
X ( T )= p:v(0)(2/n2){ In (T*/T)+const. (38)
552 L.P. GOR’KOV [CH. 7,O 5

The plot of the magnetic susceptibility, 1, for V3Si and N3Sn versus 1nT is
drawn in fig. 19. These results look like strong evidence in favour of the
existence of the well pronounced singularity (32’) in the best samples of
Nb3Sn and V3Si.

25 50 75 100 150 200 250 300

T(K1
Fig. 19. The magnetic susceptibility of V3Si (Maita and Bucker 1972) and Nb3Sn
(Rehwald et al. 1972) plotted in Gor’kov and Dorokhov (1976a) as a function of 1nT.
The numerical values for xv3si have to be multiplied by the factor 181/51 to correct the
arithmetic error of Gor’kov and Dorokhov (1976a).

It is also worth pointing out that the singularity in the density of states
can change the ordinary linear in T contribution to the specific heat caused
by electrons. In full correspondence with (38) one would have

where C,,(T) is the linear in T term

C,,(T) = +n2v(O)T

for the flat dispersion law.

5. Structure properties of the A-15 compounds in the simplest model. Phonon

spectrum

We have seen that because of considerable complications in the mathematical

part of the problem [see eqs. (21), (21’) and (2191 any attempts to develop
CH.7.8 51 PROPERTIES OF A-15 COMPOUNDS 553

a completely microscopic theory for the A-15 compounds look rather

hopeless. Therefore in our analysis of the structural and superconductive
properties we shall oversimplify the problem, considering it from the ‘three-
dimensional’ point of view. We suppose that the 3D effects have restored the
Fermi liquid picture of well defined quasiparticles which is usual for the
description of the ordinary metal properties. If Tcrit, eq. (22), is of the order
of the characteristic phonon frequency (200-300 K), as could, in principle,
be expected, then at T, N 20K and T, N 20-50K one still has a tem-
perature range where such an approach seems to be selfconsistent at least
qualitatively. The basic role of the initial one-dimensional picture is reduced
only to the essential renormalization of interaction-blocks in eqs (21)
and (21”).
Generally speaking, the structure transformation is possible as the
‘remains’ of the one-dimensional instability - the initial coincidence between
flat electron-hole Fermi surfaces. The basic assumption for the following
treatment is that the structural instability is enhanced if the Fermi level
position lies in the immediate vicinity of the peak (32’). As was shown
above, the existence of the peak at compositions not very different from the
stoichiometric one is a specific property of the A-15’s which stems from the
choice of the term X, or X, for the electrons on weakly overlapping linear
chains. It is evident that this singularity would appear in any diagram of the
Peierls channel.
The experimental results for the magnetic susceptibility give a justification
of this suggestion. The well known strong dependence of the structural
transformation temperature on the minor details of sample preparation
(including its strong dependence on the composition) gives an additional
evidence in favour of this point of view.
According to 53, the structural transformation can be driven either by the
electronic density parameter, or by some lattice distortions of the same sym-
metry. The last concept is usually elaborated in terms of the soft phonon
mode. For the A-15 lattice there are a few modes which have the same
symmetry representation, I‘:2. One of them is the acoustic tetragonal
distortion, the others are connected with the optical phonons at k = 0,
responsible for the displacements of the transition atom sublattices. Hence,
as was noticed by Shirane and Axe (1971), one should take the coupling
between these modes into account. According to Shirane and Axe the
softening of the elastic modulus can take place even in this case.
We will now briefly repeat their argument, considering three order para-
meters: the tetragonal distortion a = a/c- 1, the sublattice displacement, u,
554 L.P. GORKOV [CH.7,f 5

and a parameter, c, describing the electronic density symmetry change. In

the harmonic approximation one has for the free energy an expression of
the form:

If only tetragonal strains are applied, the equilibrium values for u and [ are
to be defined from the conditions:

After calculation one gets the expression for the effective shear modulus:

and it is seen that (suggesting (40) is positive at high temperatures)

changes the sign, if any of the two quantities, a(T) or Oz(T),pass through
zero. In other words, Cmffbecomes soft even if C,(T)by itself does not.
The softening of the elastic modulus depends quantitatively (and some-
times qualitatively) on the choice of the driving order parameter. In what
follows, in order to simplify the calculations and to make more apparent the
peculiarities connected with the peak structure (32’), we assume that the
structural transformation is caused by the softening of C,(T) by itself and
neglect all contributions which come from coupling with the other degrees
of freedom (u and 0. In particular in the Hamiltonian (7) for the one-
dimensional electron and its three-dimensional version (23), (23’) and (25) :

in the general expression for the electron-phonon interaction

we will omit all terms with y, d, and d3 (we discuss this approximation
below). All corrections to the electron-phonon interaction of fig. 13b are
also neglected. Certainly if the quantitative side of the matter and comparison
CH. 7,5 51 PROPERTIES OF A-12 COMPOUNDS 555

with experiment is kept in mind, taking account of all these factors could
be very important.
If we restrict ourselves to the tetragonal distortion a = a/c- 1 along z:

E,, = E~~ = 3a; E,, = -$a, (42)

then the ‘lattice’part of the elastic energy

can be represented in the following way

The electronic contribution to the elastic energy comes from the terms
quadratic in strains in the expression for the electronic thermodynamic
potential:

In this expression the sum is taken over all three sets of chains (i), the index o!
labels the two branches of the spectrum (25). If the chemical potential lies
in the neighbourhood of one of the peaks (32), one can use the simplified
expression for the electron energy (33):

which is responsible for the singularity in the density of states. In this way
one gets the i-chain contribution to the potential ~562~:

d,a+
here for the x-chain, for instance, h(,) = d , ( e y y - ~ , , ) + ~ B ( ~=- H )
pB(a-H)and includes the terms with the magnetic field. The integration
556 L.P. GORKOV [CH.7,O 5

over E is defined schematically in the sense that we will be interested in the

elastic contributions which are not dependent on the exact energy limits of
integration. For the same reasons we shall not define the constant in (44)
under the sign of the logarithm.
After straightforward differentiation of expression (44) for the x- and
y-chains and combining the result with the lattice contribution one obtains
for C,(T) in the cubic phase (at H = 0)

where Go)is the transformation temperature at p = 0 (i.e. when the Fermi

level is exactly at the position of the peak (32)). TLo' is defined by the
condition

and a function s(x) has been introduced

The asymptotic behaviour of s(x) looks as follows:

s(x) =
-7<(3)2/4n2; x < 1,
(46')
-In(2yx/a); x $ 1.

Using eq. (37) for all three sets of chains we get for the magnetic suscepti-
bility

Therefore in the cubic phase within the framework of this approximation

there is a relation between the temperature dependence of both quantities:
CH. 7,$ 5 1 PROPERTIES OF A-15 COMPOUNDS 557

Let us accept the notation A(T) = dlct(T) and expand the thermodynamic
potential in the deformations up to terms of the fourth order:

651 = -${[In (~)+s(~)]A’+sw(~) &}. (48)

Equation (48) is the expansion for the thermodynamic potential usual in

the Landau theory of second order phase transitions. In our case 662 (48)
defines the growth of the spontaneous tetragonal distortion a(T) in the
immediate vicinity of T < T,. For p = 0 (when the singularity (32) is most
pronounced) one has

and
4 T:)-T
c, = dfV(0) -a2
. TE)
Expression (45) also defines the dependence of T, on the composition. For
smallp/T 6 1

AT,/T&” = -(71;(3)/4d)@/TLo))’. (51)

From eq. (48) the change of T, can be found when external deformations
are applied:

A T,/TE) = -(75(3)/4~’)(d~ct/T~’>~. (49’)

It is known (Maita and Bucker 1972; Dieterich and Fulde 1971;Williamson
et al. 1974; Ting et al. 1973) that the temperature of the martensitic trans-
formation is rather sensitive to the external magnetic field. Using (44)with
H # 0 it is easy to derive the following expression for the shift of martensitic
transformation temperatures in the presence of a field:

ATmITm = -P(pBH/Tm)’, (51’)

with
558 L.P. GOR’KOV [CH. 7,9 5

At p = 0 we have /? = 7C(3)/4nZ N 0.21, which is close to B = 0.217 of

the Labbe-Friedel model (Dieterich and Fulde 1971). If 1p\ increases, the
value of /? decreases:

B = 0.21[1 - 0 . 1 6 ~ / T ~ ’ ) 2 ] ; (PIT 4 1).

There are few data for V,Si: /? = 0.15f0.01 (Maita and Bucker 1972) and
/? = 0.101f0.02 (Williamson et al. 1974). The dependence of /? on the
quality of the samples has been confirmed in Williamson et al. (1974).
Let us turn to the tetragonal phase. Instead of expansion (48) one has
now d ( T ) TZ’. Straightforward calculations of (44)are still possible. In
N

this way one gets for the shear modulus corresponding to the tetragonal
deformation (42) below T,,, the following expression:

C, = -dlv(0)- f2{ In-++

T; [-
s( “ y ) + s ( q J . (45’)

The expression for the magnetic susceptibility becomes:

As was already mentioned, both these expressions are also correct at all
temperatures if the tetragonal distortion is caused by some external strains.
In the absence of stresses the magnitude of d ( T ) in these equations should be
defined from the equilibrium conditions :

which can be expressed in the form

T’: E-P-A
=4
i m

1- m deln- I4 P T - t h -
E-P+A
2T
+-AT ch-’ -
2T
(52)
CH. 7,g 51 PROPERTIES OF A-15 COMPOUNDS 559

(The right-hand side of eq. (52) actually does not depend on the cut-off value
under the sign of the logarithm.) In fig. 20 the result of the numerical solution
of eq. (52) is shown (at p = 0). The dashed line represents the experimental
X-ray data for Nb,Sn. At T = 0:

C,(O) = (2/d)d:v(o). (53')

1.0

0.8

0.6
h
0
v
5
\
iz 0.4
Y

0.2

0.2 0.4 0.6 0.8 1.0

TIT,

Fig. 20. The square of tetragonal distortion az(T) = (a/c- 1)2 calculated using eq. (52)
at p = 0. The dashed line represents normalized experimental data for Nb3Sn (Maiifert
et al. 1967).

The relation (47') between x(T) and C,(T) is violated in the tetragonal phase.
In this connection it is interesting to point out that at low temperatures (if
p = 0) the expression for the magnetic susceptibility takes the form

The logarithmic term in this expression has its origin in the fact that at the
tetragonal transformation (42) only two chains are distorted. Therefore a
similar term enters the elastic modulus which is responsible for the deforma-
tion E,, = -eYy in the tetragonal phase.
560 L.P. GOR’KOV [CH.7,O 5

Let us once more emphasize the essential difference between the results
obtained above and all the Labbe-Friedel type models and their picture of
the Jahn-Teller effect consisting in the redistribution of electrons between
different chains. Though the density of states peak (32), (32’) plays an
important role in our treatment of the structural transformation, there is no
considerable redistribution of the occupation numbers of electrons between
the three sets of chains (in comparison with the initially large number of
carriers on each chain).
In all the previous calculations we have neglected the change of the chemical
potential caused by spontaneous (or by external) distortions. As a matter of
fact at this transformation the new position of the chemical potential should
be defined from the condition that the whole number of carriers which is
determined as

(where the sum of the contributions from all chains is to be taken) has to
remain unchanged after distortions. The investigation of the equation

N = const+ vI(e, A, p)n,(&)ds,

I

where n&) are the Fermi functions for the electron occupation numbers on
different chains, shows that the corresponding change of the chemical
potential position has the form

and is comparatively small due to the presence of the large logarithmic

factor ln(T*/T,,,) % 1. However the change of the chemical potential must
be included into the calculations pretending to describe the quantitative
behaviour of A-15 compounds. For instance, the curve

shown in fig. 21, has been calculated as a function of the Fermi level
position, po, in the cubic phase at T = 0; namely this po is the true charac-
teristic of the chemical composition.
In the cubic phase the function ?(T/po)is responsible for the temperature
variation of both the magnetic susceptibility and the shear modulus C,.For
this last quantity the dashed line represents the logarithmic contribution
CH. 7,451 PROPERTIES OF A-15 COMPOUNDS 561

which is the only important one in the case of small po (if T/po+ 00, i.e.
the chemical potential coincides with the position of the singularity (32)).
The horizontal line contains the ‘bare’ lattice contribution at a fixed com-
position, po , and is normalized in the appropriate way [see eq. (45)] :

-0.51 /I I

I
I
-1.01 1
Fig. 21. Graphical definition of the martensite transformationtemperature. The function
ij(T/p,,) is defined by eq. (49, the dashed line corresponds to its logarithmic asymptotic
behaviour at large T. The horizontal line is -n2C.(0)/2v(0)d~’+ln(~~*const/2ylpo I).
Note the minima on the curve for f ( v p o ) which makes possible the first order regime of
the phase transition for some interval of compositions.

The point of intersection graphically defines the transition temperature,

Tm(po), for the structural transformation at a given composition, po .
The minimum on this curve is an interestingproperty of the C,dependence
on T and p which immediately raises the question about the thermodynamic
character of the phase transition that has been tacitly supposed to be of second
order. Before discussing the question in more detail it should be mentioned
that the common group theoretical approach (Anderson and Blount 1965)
leads to the conclusion that the corresponding transformation in V3Si and
562 L.P. GOR’KOV [CH.7, § 5

Nb,Sn has to be of first order. This fact immediately follows from the
X-ray data (Mailfert et al. 1967) in fig. 2 for the temperature dependence of
the lattice parameters in Nb,Sn;* however the question is not so clear in
the case of VgSi where the two temperatures T, and T, are rather close to
each other. Starting with symmetry considerations it is easy to construct the
following invariant of the point group Oh,of the third order in deformations

This invariant appears in the Landau expansion for the thermodynamic

potential (48) if one takes into account the terms proportional to d2 in
eq. (41) for the electron Hamiltonian. The detailed investigation in the
article by Gor’kov and Dorokhov (1976a) has shown that the electron-
phonon interactions d, and d3 are responsible for the temperatnre variation
of the bulk moduli which are known to change very slowly for Nb,Sn and
V,Si. Hence, we suppose that the ratio 9 = d 2 / 4 is small: 9 -4 1. After
simple calculation one gets instead of eq. (48):

At small p (p < T z ’ ) one has the following jump of the spontaneous dis-
tortion, asp,for the martensite transformation :

asp= 29p/d,. (55)

This mechanism of the d, interaction is responsible for the first order character
of the phase transition only at sufficiently small p. In fact, one sees that
s”(p/T) in the third term of eq. (48’) changes its sign as lpl increases
(s’’(x0) = 0 at xo N 1.91). The cause for this is clear from fig. 21 where the
~ ) plotted. If 1p1 increases, the horizontal line lies lower
function i @ “ / ~ p o is
and the point of the intersection which defines the instability of the lattice,
moves to the left. Near the minimum the existence of the two-valued solution
of the graphic equation of fig. 21 points to the first order type of the phase
transition. This is the second mechanism causing the first order transition

*In our plot of aa(T) in fig. 20 we have actually defined T, extrapolating the linear in
T,-T part of the curve above the jump a2(T = T , .
CH. 7,851 PROPERTlES OF A-15 COMPOUNDS 563

which is not connected with the symmetry arguments. For this case there are
no simple expansions like eq. (48‘) since the ‘jump’, asp, is not small. The
temperature of the structural transformation and other characteristics can
be found only by numerical calculations. Only the simplest limit of T = 0
has been considered. In this case the complete expression for 6 0 can be
written down in the closed form:

The solution of the equilibrium condition %S2/8d = 0, obtained numerically,

is shown in fig. 22. The point of the ‘transition’ (with changing composition)
is defined by SS2(p*) = 0 after substitution of A@) into expression (56).
At p > p* = 1.32(nT2’/2y) only the cubic phase is possible. The corre-
sponding ‘jump’ (the spontaneous distortion) at T = 0,
dla,,(0) = 2.27(n TE)/2y)

/
1- /
/
/
I
I
I
I
I
01 II I
0 0.5 1 1.32 1 . 5
I
111 /11:

Fig. 22. The equilibrium solution A = dla(0) at T = 0 as a fundon of p. Point

p* = 1.32(nTm/2y) corresponds to the boundary composition for the existence of the
tetragonal phase. At p > p* only the cubic phase is possible at all temperatures (the
role of superconductivity is not considered).
564 L.P. GOR’KOV [CH.7,$5

is not small in comparison with the value of eq. (53). No attempts to get the
corresponding transition diagram on the phase plane (temperature-com-
position) were undertaken for reasons which will be discussed below. The
interesting result following from eq. ( 5 9 , is the possibility for the tetragonal
deformation a/c- 1 to change sign with the change of p. Such phenomena
have been reported for the alloys Nb3Sn, -,Sb,.
In concluding this section we shall consider some other properties of the
phonon spectrum in these compounds. The inelastic neutron scattering
experiments (Shirane et al. 1971;Axe and Shirane 1973) for V3Si and Nb3Sn
have discovered a remarkable temperature softening (at cooling) of the
frequencies of phonons with wave vectors running over almost the whole
Brillouin zone. This fact is commonly believed to be closely connected with
the high T,’s in these compounds and therefore it drew considerable
attention.
Simple considerations show that this softening can be understood quali-
tatively as a manifestation of the initial picture of quasi-one-dimensional
chains. The important fact is that the softening mentioned above has been
observed for phonons with wave vector lying in the plane q = (r, v, 0). To
clarify the basic physical idea let us return to the approximation of one-
dimensional chains considered in 52. The essential feature we used in that
section was that each of the three orthogonal sets of chains provides an
additive electronic contribution to the elastic energy. Altogether these
contributions respond to the softening of C , , and C, with decreasing tem-
perature (at q = 0). If q is not equal to zero, the logarithmic terms (12) and
(13) would be of the form (for the z-chain)

depending on which is larger: T or vq,. Hence, (1) only the component of

the wave vector along the chain direction is relevant for the magnitude of
the contribution from the given chain, (2) this contribution is saturated with
the value of uq, instead of T,if uq, is larger than T.
Roughly speaking, at q = 0 all three sorts of chains take a part in the
corresponding change of the elastic energy. However, if the phonon acquires
a wave vector directed along the chain, the contribution to the harmonic
part of the elastic energy is ‘switched off. The neutron data (Shirane et al.
1971; Axe and Shirane 1973) were obtained for phonons with propagation
directions along [lo01 and [110]. Therefore even if the magnitude of this
wave vector is large enough to switch off the contributions from two chains
CH. 7,§ 51 PROPERTIES OF A-15 COMPOUNDS 565

(x and y ) the corresponding contribution from the third chain perpendicular

to them would remain unchanged in the one-dimensional model.
It is reasonable to believe that in a certain sense the same qualitative
explanation of the phenomena would still be correct, at least as long as each
of the three orthogonal sets of chains gives an additive contribution to the
elastic energy. The simplest verification of this suggestion would be the
experimental study of the temperature dependence of the frequencies of
phonons with wave vectors having three non-zero components. As far as it
is known, there are no data for phonons with propagation direction along
[lll].
Evidently, these qualitative arguments have to be confirmed by straight-
forward calculations based on our theory taking the three-dimensional
character of the electronic spectrum into consideration. It means that, as a
result of calculations, we should obtain the right sign of the effect (lowering
of frequencies at cooling) and, on the other hand, the effect of softening if it
exists, has to be most pronounced in the vicinity of the peak in the density
of electronic states. We shall not go into all the details and limit ourselves
to a description of the main steps in the calculations (Gor'kov and Dorokhov
1976a). It is supposed that the temperature is low (T << T*), therefore in
what follows we look for the major terms in T/T*. In correspondence with
the comments in $ 3 we need the expression for the polarization operator,
n(q,T), defining renormalization of the phonon frequency. For the general
case it can be written in a closed form using the electronic Green's function

= (const/4ni) j j j j ( & ~ ) ~ d z th
d ~(2/2T)
p

x HTr [WR(p+
z)WR(p- z>-c.c.l>,
(57)
where p+ = pkjq.
Integration over d3p, owing to the pole behaviour of both Green's
functions, is actually restricted to the momenta region close to the corre-
sponding Fermi surfaces. The last ones, in turn, are situated in the neigh-
bourhood of the cubic Brillouin zone faces. Integration in eq. (57) over the
three different pairs of zone faces corresponds now to the above mentioned
fact that the contributions from the three sets of orthogonal chains are addi-
tive. The 2, matrices have appeared due to the interaction term c& in Peph(41).
566 L.P. GOR’KOV [CH. 7,$5

Before writing down the explicit expression for the electron Green’s functions
it is convenient to simplify the notation. For the x-chain we use:

a = T*(cos2q+cosz@)+p; c = ~*(cos~q-cos~~), (58)

and

The Green’s functions on the respective faces are the solutions of the matrix
equation

with the Hamiltonian

A = -a2+ud,ty-ct,.

The solution is of the form:

6 ( p , z ) = [(z+4 2 + us,.ey - ct,][(z+ - (udJ2 -CZ]- l . (60)

The simplest case in the general expression (57) corresponds to phonons with
wave vector q along one of the cubic edges. For instance, let us take
q 11 [Ool]. In this case the contribution to the elastic energy proportional to
EZ,(q) in the harmonic approximation comes from both x- and y-chains.
The result of the calculation has been represented in the article by Gor’kov
and Dorokhov (1976a) as a dispersion law for the elastic modulus Cll(qZ):

This modulus is responsible for the propagation of longitudinal phonons

along [Ool]. The integral factor in eq. (61) varies slowly from 1 at qz = 0 to,
approximately, 0.75 at q, = n/a. The softening of these phonons at all
qz’s has the same order of magnitude as the softening of the acoustic shear
modulus C, at q = 0. It is easy to explain the mathematical reason for this
large contribution, noticing that in this special case the poles of both Green’s
functions can be taken in the form (33) along the whole edge of the cube
CH.7,g 51 PROPERTIES OF A-15 COMPOUNDS 567

because the wave vector q = (Ooqz) enters only the function cos(+p,a) in
this last expression.
If the wave vector q is moved from the [Ool] direction, the logarithmic
contribution to eq. (61) disappears due to the fact that now in the Green’s
functions G(p+)and G(p-) two poles cannot be chosen on one and the same
line connected with singularities in the density of states. From eq. (33) it is
seen that for instance, the x-chain contribution behaves differently in
dependence on whether this move occurs in the plane (z, x) or (2, y). In the
first case a drastic decrease of the contribution from the x-chain takes
place at

q,u > (TT*)”~ -

In the second case the corresponding criterion is

qya 2 (T/T*)”’.

The first condition determines a rather narrow cone (- 1”) of q-directions

along [Ool] beyond which the x-chain temperature dependent contribution is
completely switched off. However, if the vector q lies in the (z, y)-plane, then
even though the temperature dependent elastic contribution becomes smaller
in full correspondence with the criterion (627, and the frequency softening
must be weaker, it still exists and is quite remarkable. In this case it is
described by a more complicated expression.
Therefore, let us consider a phonon with wave vector in the (2, y)-plane:
q = (O,qyyqz)with qy,qz > qcrit, the latter being defined by eq. (62’).
Substitution of eq. (60) into (57) gives

n(q,T)= (const/4ni) JJJJ dqd$dp,dz th (z/2T)

+ +
x ([(z a+)(z a - ) - (YSx)2 +c+cJ
x {[(vSX)’-(z+p+2T* cos’ ‘p+)(z+p+2T* cos’ $+)I
x [(v6J2-(2+p+2T* COS? p-)(~+p+2T* COS’ $-)I}-’
+C.C.). (63)

It can be verified that in this case the most important term in T/T* comes
from those regions of integration in (63) where two square brackets in the
denominators are small (for example, p+2Tcos2 ‘p+ and p +2Tc0s2$- 4 1).
568 L.P. GOR’KOV [CH. 7.8 6

This condition defines two points again lying on lines connected with singu-
larities in the density of states; however, this time these lines are two different
edges of the Brillouin zone face. Considering small z (i.e. assuming T Q T*)
after some calculations one gets the following expression for the temperature
dependent contribution to the elastic deformation energy connected with
this phonon

where

and u = sinrc,, /!I= sinx,. At qz = qyl(u, /3) = 0 and one should look for
even higher terms in the expansion of eq. (63) in T/T*. The result obtained
in Gor’kov and Dorokhov (1976a) for this case, has the form of a tempera-
ture correction to the dispersion law of the shear modulus

This modulus enters in the common way into the expression for the velocity
of the transverse phonon mode (q = (2n/u)[C,5,OI; e II [lTO]) investigated
in the neutron measurements (Axe and Shirane 1973) for Nb3Sn.
Expressions (61), (64) and (65) are the main terms connected with the
singularities of the density of states. The corresponding coefficients are

-
undoubtedly exact only for the model equations (23’). At finite p the character
of the temperature dependence changes at T p. Apart from the main
contributions considered above, there always must be temperature corrections
of the order of (T/T*)2.

6. Some results concerning the superconductivityof A-15 compounds

In accordance with the concluding remarks of $ 3 and with the approach

which we have used for the description of the structural transformation,
superconductivity in the A-1 5 compounds will also be considered from the
CH. 7.8 61 PROPERTIES OF A-15 COMPOUNDS 569

three-dimensional point of view taking the curvature of the Fermi surfaces

into account. In what follows we accept the scheme of the BCS theory. It
is known that the BCS theory in spite of its mean field theory character, has
a very high accuracy. The temperature interval IT- T, I where the thermo-
dynamic fluctuations regime would be essential is extremely narrow:

ATIT, N (TJAE)’.

We cannot point out with certainty the corresponding criterion in our case.
A likely estimate can be obtained using the value of T* instead of AE as a
measure of three-dimensionality in the A-15 materials.
After this short comment let us turn to the Cooper effect in systems under
consideration. In the common approach to the problem one usually leaves
only the phonon-induced part of the electron-electron interaction. The
reason for doing so is that this interaction in some sense is a ‘long range’
interaction.* As a consequence, the repulsive interactions enter into the
expressions for T, weakened by a factor lnAE/wo. Keeping to this scheme
we will, however, suggest that the phonon-induced interaction is already
renormalized by all the effects of softening considered above. The matrix
element in the right side of eq. (21’) has the schematic form:

where the integration over d3p at the last step is separately performed over
the energy variable, the distance u = e(p’)-p from the Fermi surface
(0 (wChar)),and over the Fermi surface. The former is just responsible for
N

the Cooper effect, i.e. the logarithmic enhancement of the interaction

constant &,at low temperatures. (The cut-off procedure coincides with
that acc‘epted in the BCS theory.) The second integration becomes non-
trivial for anisotropic systems. As was pointed out in Pokrovskii (1961), for
the last case the critical temperature has to be defined from the solution of

*The retardation effect in eq. (18) results in correlation between electrons after the
electron-phonon scattering which holds for time intervalsof the order of ti/wo. In the case
of short-range interactions of a Coloumb nature this time scale would correspond to
atomic units.
570 L.P. GORKOV [CH.7 , $ 6

the homogeneous integral equation for a small anisotropic energy gap

A,(p) with the kernel of the general form

and A,@) is dependent only on the position of the momentum p on the

Fermi surface. Equation (66) represents the pole-like solution for the vertex
r in the anisotropic systems.
The complications in the solution of the problem in our case arise on two
accounts : the non-trivial dependence of the integrals over the constant energy
surfaces on the given distance from the Fermi surface (fine structure of the
electron spectrum) and the large number of different branches of the spectrum
(three sets of chains). The second question has no principal significance
(‘two band’ models have been studied by many authors; see, for example,
Moskalenko 1966); however, it makes the resulting equations quite cumber-
some. As for the shape of the Fermi surface, we have already mentioned that
its main parts are located close to the corresponding faces of the Brillouin
zone (the characteristic distance US T* ) . The behaviour of the Fermi
N

surface near the edges of the cubic zone is described by eqs. (34), (34‘).
The schematic equation for the pole in the Cooper block shown on fig. 23,
contains matrix Green’s functions which are matrices of the sixth order. We
will label the single elements of the latter, G$’, by two pairs of indices. The
upper pair represents the type of chains (i.e. along (x, y, z)), the pair of Greek
indices below appears as a consequence of the twofold degeneracy of the
electron representation at the point X.On the main part for each of the three
pairs of zone faces only the corresponding terms, G$) are large.
To simplify the problem we suppose that the vertex of the dashed line in
fig. 23 is diagonal on the chain index. In other words, we neglect the phonon-
assisted tunnelling of electrons between chains: after the process of electron-
phonon scattering the electron is left on its own chain. Therefore the two
ingoing lines (p, - p ) in fig. 23 have identical indices (i), and this gives the
possibility of introducing three matrices of the ‘superconducting gaps’:

In the absence of non-diagonal contributions from G$)(i # k) to the internal

part of fig. 23 one would get the picture of three independent superconducting
parameters for each of the three orthogonal sets of chains. The straight-
CH. 7,5 61 PROPERTIES OF A-15 COMPOUNDS 571

forward calculation of the contribution from the non-diagonal elements

shows that the coupling between chains is actually not a weak one. The
superconductivity in these compounds has all the essential three-dimensional
features.
It is well known that the phonon-mediated electron-electron interaction
is short range in space. Nevertheless, the vertices of the dashed lines, which
represent the corresponding deformation potentials, are dependent on the
phonon wave vectors (on the atomic scale). The Hamiltonian Pcph (41)
contains the interaction of electrons with phonon modes at q = 0. The
generalization of (41) is self-evident:

where thefi are linear in distortions of the lattice (tz would correspond to the
representation A; of table 1 which changes sign when t + - t and therefore
is not present in eq. (67)).

Fig. 23. Diagrammatic form of the equation for the pole solution in the Cooper-type
channel, defining the critical temperatures of the superconducting phase transition. Only
a phonon-mediated electron-electron interadon is included.

Let us now write down the right-hand side of the equation shown in
fig. 23:

and carry out some simplifications making possible its calculation. If the
singlet-type of Cooper pairing is chosen, the superconductive gap has to
contain only combinations symmetric in a, fl:
512 L.P.GOR’KOV [CH.7,5 6

Before substituting (69) into (68), one should accept an additional assump-
tion concerning the averages ( f f ( q ) ) proportional to the corresponding
D-functions. Namely, we will neglect their q-dependence, i.e., both inter-
acting electrons are to be on the same chain and, hence, A,@) = const.
With this assumption we lose an essential part of the cubic anisotropy of
the real crystal. Nevertheless this seems to be the only possibility in order
to get any results without numerical calculations.
For the beginning we start with the calculation of the diagonal terms
in eq. (68). After substitution of (69) and the expression (60) for the
Green’s functions, G$’, and after some simple matrix calculations, the
diagonal part of (68) can be represented as follows

The denominators of the Green’s functions in the last expression, according

to the BCS theory (see the derivation of (66)), provide the logarithmic
dependences on temperature near the corresponding Fermi surfaces. The
combinations A, B, C have the following form:

First of all one sees that the equation for #’ is split off from those for
(a!), 8:)). An interesting question arises in connection with different signs
before ( f f ) in the square brackets of eq. (70). Let us recall that for the
:)
phonon-induced interaction the (+)-sign at (f corresponds to attraction
[(ff) < 0, see eq. (18)].Therefore, if only the phonons are taken into con-
sideration, then most likely yo = 0. It is difficult to estimate the relative
magnitudes of (ff). However, comparing (at small q ) eqs. (67) and (41) one
obtainsf, = 0 andf, %. f 2 . Further we will omitf,. As for the cut-off value
in eq. (68), it is known from neutron and tunnelling experiments, that the
frequencies of the effective phonons usually never exceed 200 K (see Testardi
1973). This suggests the idea that 8 Q T*.
Expressions (70) for A, B contain the dependence on p and A = +d,a.
At an arbitrary position of the Fermi level the terms with A and p enter
everywhere together with the only characteristic scale T * . This would
CH.7.8 61 PROPERTIES OF A-15 COMPOUNDS 573

correspond to a weak dependence of T, on ~5pand deformations (an effect

of the order of (T,/T*)’). If the position of the chemical potential is chosen

of 6p and A is of the order of c’-

near one of the peaks (32), (32’)* the characteristic scale for the variations

equation of fig. 23 in a new general form

T, Q T*,8. Let us now rewrite the

where {JI) is the ‘column of gaps’ constructed from the three submlumns
a:), for each of the chains. We will write down only the row of eq. (71)
for the chain along x :

The other two equations can be obtained by cyclic permutation of (x, y, z).
The following notation and abbreviations are used: X = ln(2ye/xT), (the
combination 2y/n N 1.22 is the same as in the BCS theory for a chosen
cut-off procedure); R includes various numerical factors and the interaction
(f:)+ (fi).The matrix R‘”’is the result of integration in (70):

where

P(x) = X’+2XIn(T)+1.32,
32T* F(z) = ~ ~ ~ t h ~ z ~ u l n / l - u - z ~ ,
(74)
and G = 0.916.
We shall also need the asymptotic expressions for F(z):

*In what follows p is the position of the Fermi level with respect to this singularity.
574 L.P. GOR’KOV [CH. 7,4 6

Two ‘coupling constants’ kl ,k , come from the non-diagonal terms e(xy) in

eq. (68). The main contribution to kl and k, comes from the vicinity of the
edges of the Brillouin zone. Both kl ,k , are proportional to (T*/dE)li2Q 1.
However, in our model:

kl = (cl-In (AE/T*))(T*/dE)’’’; ,

k , = (In (AE/T*)-c,)(T*/dE)’”

contain numerical factors between 2-5 (at T* - ki ++).

N

A more attentive examination makes it possible to simplify (72) even

further. In fact, the second row of in (73) contains the term -8G.X.
Therefore, at the compensation between left and right sides of eq. (72) for
a:) one gets

or

Within this accuracy (better than -10%) the whole system (71), (72) can
be reduced to a system of three equations. Among all the solutions for
T, only that giving the highest T, is important.
Now suppose this temperature is T , b , A ) and the vector {$,} is known.
The change of T, under some perturbation l? = RO-tRlcan be obtained
with the help of the usual orthogonality condition :

+w:, Rl@,) = 0. (77)

Differentiating (73), one gets for aKfi/aT:

The two first terms in (78) are proportional to the elastic modulus C, (50)
and at T T k T, are small (of the order of unity) in comparison with the
N N

third logarithmic contribution. For simplicity we shall write all results

obtained below within this logarithmic accuracy.
CH. 7,g 61 PROPERTIES OF A-15 COMPOUNDS 575

We shall determine the dependence of T, on deformations in a cubic

sample (a:' = a:' = a:)). For a tetragonal distortion A, = fdla which
touches only the chains along x and y, one gets from (77) and (73)

(here we have also used the relation aF(z)/az = -(2/z)s(&)). If p is small

enough 5 TZ), then AT, < 0. For p = 0 (T,(O) = Tco):

Comparing eq. (79') with the corresponding dependence of T, (49') one

sees that the factor 31n(64yT*/nT',) in the denominator of eq. (79') reflects
in the correct way the weaker sensitivity of T,to deformation. The quadratic
dependence of T, on a was observed for V3Si (see Testardi 1973, eq. (11)).
--
Using his experimental data and the value dl 1 eV one obtains the
following estimates: ln(MyT*/nT<,0))N 7-7.4 and T* 500-800 K.
In the tetragonal phase or for samples deformed by an external uniaxial
stress, the new symmetry of the crystal is reflected in the symmetry of super-
conducting gaps:

in the limiting case of large applied strains the highest T, corresponds to the
z-row of the matrix R, i.e. to the z-chain where the dependence on A = fdla
is absent. Using the asymptotic expression for F(z) (75) at A % Tone gets

A = klX/F(A/2T,) N k, In (2yO/xT,)/ln2 (2yA/xT,) 4 1. (81)

- - - -
To understand the order of magnitude of external deformations needed to
get a strong enough inequality (81) we shall take d = d1q,, 8 (8 UH)K),
kl 0.1 (at T*/AE 1/50-1/80for V3Si). Onegets A ;5 0.1 at or, 2 x lo-'
N

(compare this with the spontaneous deformations ay,sl = 2.5 x and

aNbrSn =6.5~
Let us now turn to the problem of the very high upper critical fields,
H c z , in these materials. Using eq. (77) we shall restrict ourselves to the
interval IT-T,I 4 T,. To find the value of H,, in this temperature range
one should derive the corresponding Ginsburg-Landau equation for the
576 L.P.GOR’KOV [CH. 7,fi 6

coordinate dependent parameter $(r). The procedure (Gor’kov 1959)

consists in the substitution of

into eq. (68) for the Fourier component, [$,I, and the subsequent expansion
of the right side up to terms of the order of (qu/T,)’. Simple calculations
give the contribution to KiY of eq. (73):

(The last coefficient comes from the integration over the whole Fermi surface,
far from edges. Its exact expression is therefore dependent on the choice of
the model spectrum (25). At the same time it has not to be sensitive to small
deformations and to the variation Sp.)
The Ginsburg-Landau equation for the wave function [$(r)] =
$(r)[A, A, 11 can be immediately obtained from (77):

LIT(T+U’
aKl‘i’ aKp)
-)$(r)
aT

- 7GC(3)u2
4n2T:
{(
-1 .-
a --
az
2e A ,
c
>I
+A’ (- i V - - ’r A)2}
* $(r) = 0. (82)

(We use (”) to label the vectors in the (xy)-plane.) This equation can be
compared with the one for the BCS theory (Gor’kov 1959):

Equation (82) being rewritten in the same form, gives for the cubic phase

481c’T: 48n’T:[ 1 64yT*]

+- -1n-
7f;(3)$ 7[(3)vz 2G nTko’

The factor in the square brackets reflects the peak (32) (or (32’))in the density
of states. It is interesting to compare the values of H,, for pure Nb or V
and Nb3Sn and V3Si. Due to differences in T, and larger densities of states
(smaller Y’ and the large logarithmic factor) one gets an enhancement of
He’by a factor of about 20-30 if compared with the transition metals.
CH.7.8 61 PROPERTIES OF A-15 COMPOUNDS 577

A very interesting situation corresponds to the limiting case (81) of large

external deformations (A Q 1). Instead of (82) and (83) one has the equation

has the anisotropy HLk' - -

which reflects the anisotropy of strains in the form of the anisotropy of the
G-L effective mass tensor* mtfl m$rA-2. Since the critical field, H c 2 ,
(mlmk)l'', one sees that the enhancement factor is
proportional to A-' for H i and to for This could be the likely
explanation for the large critical fields observed in real crystals of A-15
materials. In commonly occurring samples large enough internal stresses
exist. The mean critical field is mainly defined by the component H:2. In
any case this mechanism can compete with the commonly accepted impurity
induced increase of If,, .
The results obtained above contain the well-known experimental fact that
though T, is sharply dependent on the composition, the correspondingchange
of T, is not catastrophic. At A t = 0 (no deformations) we get the equation
for T,Q <a:' Q a:))

At small p one again obtains the same large logarithmic factor in the
denominator :

*The picture under discussion has some features in common with what was obtained
for weakly coupled linear chains in the Labbe-Friedel-Barisit model (BarisiE and
DeGennes 1968) though there are many differences in the underlying ideas. We only note
that in our case the anisotropy of the effective mass tensor in the G-L equations is due to
the coupling between chains and not to the intrinsic anisotropy of the three-dimensional
electron masses (Barisit and DeGennes 1968). This anisotropy is too large (- T*/AE
to be taken into account in eq. (84).
518 L.P. GOR’KOV [CH.7,66

Let us also discuss in a few words what happens with T, at structural

transformations. In fig. 24 both T, and T, are schematically plotted as
functions of the composition y. The dashed parts for each curve are supposed
to have been calculated in the absence of the second phase (for instance,
eq. (85) for T,). To the left of the point of intersection, y < yS,, the develop-
ing spontaneous deformation will suppress T, in accordance with eq. (79).

I
I-1 s i n P

Fig. 24. Behaviour of T, and To is shown schematically as a function of electron con-

centration (with chemical potential as a measure of doping). The dashed parts of both
curves have no physical meaning as long as competition between two phases is neglected.
At p < p,,,, a small but sharp drop of T, is expected as a result of the finite spontaneous
deformations developed after the structural transformation (see eq. (55)).

We have already shown that the martensitic phase transformation is actually

of the first kind. Therefore for y = psm the jump in the deformation will
result (neglecting fluctuations) in a jump of To.This sharp decrease of T, at
the boundary of the cubic phase has been observed (Berthel et al. 1975) for
V3Si (AT, 0.3K).A similar behaviour (a maximum T, just at the boundary
N

between tetragonal and cubic phases) has been reported for Nb,Sn, -xAlx
alloys (Vieland and Wicklund 1971) (AT, I K, see Testardi 1973).
N

The discussion above has shown that all these effects can be explained on
the basis of modified BCS theory. There is no need to introduce new
mechanisms of ‘the enhancement of superconductivity by the structural
instability’. This question is often discussed by many authors (see Testardi
1973; Wcgcr and Goldberg 1973).
CH.7,g 71 PROPERTIES OF A-15 COMPOUNDS 579

It is reasonable, however, to put forward the question what conditions are

the most favourable for superconductivity in this or that compound. The
results obtained above show first of all that any internal strains have to be
removed (by heat treatment) and the composition should be as close as
possible to that corresponding to the boundary of the cubic phase. In the
preceding section we have discussed the remarkable softening of the phonon
modes which has to occur for some phonons with wave vectors lying in the
plane (I 10). According to the familiar McMillan interpolating expression for
the effective interaction constant of the BCS theory, interactions (or
c f 2 ( q ) ) in our equations) are proportional to the mean value of (0-’(p-p’))
where ( ...) means an average over the positions (p; p’) on the Fermi surface.
The quasi-one-dimensional character of our model immediately means that
the Fermi surface is very close to the planes (110) where the softening of
phonon modes just occurs. As we have proved, a considerable magnitude
of this softening should be expected in the narrow strip (62’) near the edges
of the zone, if the position of the Fermi level is close to the peaks (32), (32’).
Being unable to give a numerical account for the contribution of this effect
to the value of To we note only that the mere existence of this effect points
in the right direction. This effect, by itself, is a manifestation of the ‘parquet’
peculiarities discussed in 5 3.
In conclusion of this section we point out that within the framework of
the suggestions accepted above (namely, that the superconducting ‘gaps’
a:”(p) = cry’ are not dependent on the position p on the Fermi surface) a
complete theory of the superconducting phase can be developed. However,
the considerable anisotropy of the energy gap for these compounds (see
Testardi 1973; Weger and Goldberg 1973; Izumov and Kurmaev 1974)
perhaps cannot be adequately described in the approximation considered
above being the result of the anisotropy of interactions in eq. (66).

7. Discussion

It is interesting to compare some physical consequences obtained in the

preceding sections with the available experimental data. We do not pretend
to do a quantitative comparison since many of the factors have been omitted.
However, one will see that qualitatively the theory in its main aspect gives a
self-consistent interpretation for the unusual properties of these compounds.
Tn the range of coexistence of superconductivity and tetragonal distortions
the derivation of any analytical expressions in the tetragonal phase below To
580 L.P. GOR’KOV [CH. 7, # 7

becomes rather difficult.* Therefore most of our results concern the structural
properties. Strictly speaking only Nb,Sn provides a sufficiently wide tem-
perature range for the existence of the non-superconducting tetragonal state.
Even in this case we will not try to get any complete and general results, since
it would involve us in the study of interactions and competition between
different order parameters: tetragonal distortions, sublattice displacements
and electronic density waves. Such a general formulation of the problem
would make tedious the analytical approach (in any case this goes beyond
the scope of our review paper). It seems that owing to the large number of
free parameters it would be easier to develop a quantitative comparison with
the experimental data on the basis of a more phenomenological description.
Instead of doing this, we will concentrate our attention on the physical
manifestation of the density of states peak (32), (32’) which, providing it
exists, could play an important role in any choice of the driving order para-
meter.
We have already pointed out in 0 4 that for strictly one-dimensional chains
there is no logarithmic enhancement of the magnetic susceptibility within
the first approximation in the interaction constants. Therefore the ob-
served temperature dependences in Nb,Sn and V3Si have to be ascribed
to the varying density of states in eq. (37). An alternative (or additional)
explanation which in our A-15 structure is connected with the unusual
role of impurities by themselves will be discussed briefly below.
The plots of the magnetic susceptibility for Nb,Sn and V,Si versus 1nT
in fig. 19, if compared with eq. (38), give the densities of states for uncoupled
chains, respectively, v(0) = 6.7 states/eV.atom and v(0) N 13 states/eV*atom
(at 6 = 1). These are rather large values, as are the values v(0) N 6.5 states/
eV-atom and v(0) N 9.2 states/eV.atom for pure niobium and vanadium
(according to the magnetic susceptibility data; see Gladstone et al. 1969),
and would correspond to rather narrow energy bands. For the widths of the
latter an estimate using the photoemission data (Kurmaev and Nemnonov
1971) gives for V,Si AE N 3-4 eV. One can reconcile the large values v(0)
obtained from the data of fig. 19 with these estimates of the band widths

*As long as the superconducting gap does not depend on the point on the Fermi surface,
the extension of the corresponding formulas of the BCS theory presents no particular
complications. It is known, however, that the superconductivity in these compounds is
quite anisotropic. As was mentioned,the gap anisotropy is connected with the dependence
of the interactions on momenta along the F e d surface. In the light of the comments in
the preceding section concerning the role of the phonon modes ‘softening’ and its sharp
dependence on wave vectors this fact could be. of principal significance.
CH.7,s 71 PROPERTIES OF A-15 COMPOUNDS 581

introducing as a possible explanation either the ordinary Coulomb mechanism

for the enhancement of the magnetic susceptibility, or the contribution from
the additional peak in the density of states connected with impurities (see
below).
In the simplest version of the theory (Gor'kov and Dorokhov 1976a) the
deformation potential dl can be estimated from eq. (45) if we take the
temperature behaviour of C, at temperatures higher than. '7 In this way one
gets dl = 2.5 eV for Nb,Sn and dl = 1-1.5 eV for V3Si. Other independent
posibilities are available in principle, for the definition of d l . For example,
in the cubic phase eq. (49) defines the change of T, under applied external
stresses. Expression (48) for the thermodynamic potential leads to the
anharmonic correction to Hooke's law. The accuracy of the existing data is
still insufficient for a successful comparison with the theory. However, for
instance, for V,Si, with the help of eq. (49), describing the temperature
dependence of distortion near T,, a rather close value of dl N 1.1 eV can
be obtained. One of the main uncertainties is that in all the previous expres-
sions the parameters 7 '
:) and p are actually unknown, being dependent on
the quality of the sample. (For instance, the procedure of heat treatment
determines the distribution of internal strains which are very important in
many respects). This fact finds its reflection for example, in the irrepro-
ducibility of the results of experiments devoted to the dependence of the
martensitic transformation temperature on the applied magnetic field.
According to eq. (51') the coefficient jl depends on p. At the same time B
also changes strongly in the presence of any internal stresses.
In our opinion, any detailed comparison with experiment is justified only
if the complete set of data for the magnetic susceptibility, elastic moduli,
tetragonal distortions, phonon spectrum etc. is obtained from measurements
on one and the same single crystal. The only example known is the various
results obtained for the single crystal of Nb3Sn grown by Hanak and Berman
(1967). In this case we have data for the temperature behaviour of the
tetragonal distortion obtained by X-ray measurements (see fig. 3). These
data are also plotted as a dashed line in fig. 20 together with the theoretical
curve calculated at p = 0. From eq. (53) it is easy to get the independent
estimate of dl N 1.6 eV. This smaller value of dl obtained in this way, could
be understood as the result of the arrest of the growingtetragonal deformation
by the onset of superconductivity. One should also keep in mind that the
phase transition at T, is actually of the first order (see, however, the dis-
cussion below of the low temperature behaviour of the elastic moduli for
Nb,Sn and V3Si).
H
 582 L.P. GOR'KOV [CH.7,s7

For the magnetic susceptibility a sharp decrease below T, is typical.

Using eq. (54) for x at T N T, one succeeds in getting a value for this jump
quite close to the result observed in Nb,Sn (Rehwald et al. 1972).
A more interesting fact concerns the difference in the low temperature
behaviour of the elastic properties for V,Si and Nb,Sn. For the former the
shear modulus becomes finite below T, but is still small at all lower tem-
peratures. Leaving aside the question of the role of the superconductivity
which has approximately the same characteristic energy scale, let us point
out that such behaviour is typical of the concept of the 'soft phonon mode'.
'
In this concept the initially unstable phase with a small negative 'bare square
of frequency', oi < 0 at the low temperature transition goes over to the
stable phase with the positive value w& > 0. This last quantity is, as before,
of the order of Ioi(T T,)I. To illustrate this important idea, we take as
N

an example the expression for the renormalized shear modulus C,[eqs. (457,

deformation d ( T ) = +d,a(T) T,.-

(53')l. At T < T, the logarithmic dependence is saturated by developed
Hence, at T < T,, C,""(T)
Crb(T,) < C, (T = 300 K). The softness of the elastic shear modulus C, for
N

V3Si at low temperature appears therefore as evidence that in this compound

the martensitic transformation is driven by tetragonal distortion. The fact
that both transitions in V3Si have almost identical critical temperatures
(T, N 20-25 K ; T, N 17.5 K) seems in this scheme rather incidental since
the transition temperatures were not calculated.
In the Nb,Sn case the shear modulus C, at low temperature increases
again in magnitude, exceeding the room temperature value (Rehwald et al.
1972). If this result is not caused by some experimental uncertainties, the
experimental data are in apparent contradiction with the predictions of
eqs. (45') and (53'). The large value of C,at T = 0 cannot be explained either
by introducing a finite p or by taking the first order type of the structural
phase transition into account. The restoring of C, at low temperatures can
be explained in terms of eq. (40). Since it is experimentally known that
optical phonon modes do not become soft, the natural explanation consists
in the suggestion that for Nb,Sn the ruling structural order parameter is of
electron origin, in accordance with the discussion of 5 5. The softening of C,
is forced and takes place only in the temperature interval where the denomina-
tor in eq. (40) tends to zero.
A very important problem for the understanding of the properties of the
A-1 5 structure materials is the role of contaminations and defects. Numerous
investigations (see Testardi 1973) have shown that almost all properties are
extremely sensitive to alloying or violation of the stoichiometry. The results
CH.7,871 PROPERTIES OF A-15 COMPOUNDS 583

can be summarized as follows: at substitutional alloying the properties are

much more sensitive to the substitution of transition atoms than non-
transition ones. This conclusion is perhaps, the only straightforward indica-
tion of the unique role of the transition atom chains. From the point of view
of the theory which starts with the picture of one-dimensional chains, one
has to distinguish between two different limiting cases. If in the A3B com-
pound the atom B is substituted (like Nb3Sni-,Sb, or Nb,Sn,-,Al,) the
main effect is an increase or partial decrease in concentration of conduction
electrons in the chain. A secondary effect would consist in the backward
scattering of the conducting electrons. If the latter is small the description
of alloys using only the parameter p - the chemical potential position -
would be adequate. Let us check that the existing experimental data for this
type of alloys are consistent with our picture. In fact, for Nb3Snl-,Al, the
boundary of the tetragonal phase existence corresponds to x S 0.075
(Vieland and Wicklund 1971). The corresponding change, dp, of the chemical
potential is estimated from

-
at x = 0.075it would be dp 30 K T,. We have already had a chance to
N

mention that for Nb,Sn,-,Sb, the sign of tetragonality changes at x = 0.15.

From one side it is again a reasonable estimate for dp. On the other hand,
the estimate (86) is, to some extent, uncertain. Indeed, it is only slightly
changed, if we substitute for the density of states the expression (32) in the
neighbourhood of the peak, since the prefactor (2/nZ)compensates in a
considerable way the magnitude of the logarithm.
The second limiting case in the one-dimensional approach corresponds to a
substituted atom or defect in the positions of the transition element atoms.
Such a configuration could 'lock' the electron motion along the chain and
would therefore demand a three-dimensional mechanism for the electric
current. The backward scattering effects would be the most important in this
case.
Even in the first case the main question remains whether at x = 0 p lies
close to the peak (32). It is possible to get some idea about how p is changing
in dependence on stoichiometry violation, if we again use the estimate (86)
and substitute for its right-hand side 6xp instead of 2x. Here,p is the number
of electrons supplied by the transition atom to the conduction band. Hence,
in this case the change of p is several times faster. It is worth mentioning
that in the process of preparation of A-15compounds their chemical com-
584 L.P. GOR’KOV [CH.7,9 8

position is known rather approximately. The common practice for the

selection of the so-called ‘stoichiometric’ samples consists in the measure-
ments of the residual resistance. Unfortunately we are not able to suggest
any theoretical expression for this quantity. This problem is especially
di5cult for one-dimensional objects. Beside the famous Mott localization in
one-dimensional metals it is interesting to note an additional phenomenon
in the A-15 systems.
The linear chain of Nb atoms, for example, has an electronic band which
is similar to the half-filled electron zone for the chain with a period a* = $a
(i.e. k = n/2a*). In the process of solution the substitutional atoms take
random positions. However, these positions, z,,, are correlated along the
chain due to the periodicity and symmetry of the host matrix: z,, = a*n
where n are random integers. Hence, after averaging over impurity positions
the electron spectrum retains some memory of this correlation, which is left
in the form of an additional peak in the density of states near the point X
in our system (Gor’kov and Dorokhov 1977). Actually we are dealing here
whith a phenomenon resembling a sort of parametric resonance and con-
sisting in the appearance of Van Hove type singularities in the density of
states at ka* = in.
The height of this peak is determined by the parameters of the impurity
atom only, its width is proportional to the concentration. Apparently, such
a peak would appear in all the physical effects considered above thus making
ambiguous their interpretation. One can hope that the height of this peak is
not large numerically. To what extent this peak is smoothed out due to
three-dimensionality of the electron spectrum and how it can be dis-
tinguished in the experimentally observed quantities is now completely
unknown.

8. Summary. Some concluding remarks

In this section we would like to list again the main steps we have taken in
the course of our attempts to explain the peculiarities of the A-15 structure
materials. We have used Weget’s suggestion that in these compounds some
unexpected small parameter exists. This parameter allows us to consider
electrons of the transition atom chains in the first approximation as one-
dimensional.
The next basic assumption concerning these one-dimensional electrons
consists in the introduction of non-overlapping conduction bands of fig. 9.
CH. 7.8 81 PROPERTlES OF A-15 COMPOUNDS 585

This suggestion automatically fixes the position of the Fermi level. The band
constructed in this way immediatelyled us to the problem of stability familiar
from the theory of one-dimensional metals. The corresponding argument
reproduced in 5 3 shows that at sufficiently weak ‘bare’ electron-phonon
interaction the instability with respect to fluctuations of structural parameters
in the strictly one-dimensional case is inseparable from the superconducting
fluctuations.
In the one-dimensional approximation there is no real phase transition.
Therefore the next step would be to include some three-dimensionalfeatures
which have to restrict the regime of growing one-dimensional fluctuations.
We have considered only electron tunnelling between chains since it is evident
that the transfer integrals are to be large in the A-15’s. Even in this approxi-
mation we were unable to get a quantitative description for this transition
from the one-dimensionalfluctuations regime to the three-dimensional phase
transformation.
The structure fluctuations (and/or the corresponding electron density
fluctuations) are most sensitive to the three-dimensionality of the Fermi
surfaces. In any case, the electron tunnelling decouples the structural transi-
tion temperature, T,, and the temperature of onset of superconductivity,
T,. The question whether the three-dimensionality of the electron motion
destroys the structural phase transition or leaves T, finite, cannot be resolved
without calculations based on microscopic principles. Needless to say, this
programme in its general form looks unreal. Therefore these suggestions
show only the possibility of the structural transition being driven by the
electronic order parameter.
Assuming one-dimensionality of chains in the first approximation one
has to consider the next correction. We have done this in a straightforward
way in 0 4 by introducing an overlap between neighbouring orthogonal
chains (and neglecting all interactions). The fine structure of the density of
states arising in the tight binding model has two logarithmic peaks which
actually are non-equivalent in a more correct approach. In the general case
only the peak at E = 0 survives [see eq. (32‘)l.
We would like to emphasize that if we accept Weger’s arguments in favour
of the quasi-one-dimensionality of the d-electron motion and our choice of
the electron band structure we must also accept the peak structure which is
their immediate consequence. The structure in the form of the peak (32’)
must exist (with a reservation concerning the signs of functions v ~ ,qz,* ~ ,in
eq. (34’)); the only question is how narrow it can be in real materials and
how distant it is from the stoichiometric composition. In the presence of
586 L.P. GOR’KOV [CH.7.8 8

strains and scattering defects the peak (32’) is smoothed out (i.e. in eq. (32‘)
I E l > W).
The only result which could be interpreted as evidence in favour of the
two-peak structure consists in a ‘crater-like’ dependence of T, in the system
of alloys of NbjSn doped with elements of the IVth and Vth group (Hulm
and Blaugher 1974). In Gor’kov and Dorokhov (1976a) we kept to this
interpretation and had supposed that the T, maxima are caused by the
maximum of the BCS interaction constant due to the phonon spectrum
softening near the peaks (32). However, the results of $ 6 have shown that
this ‘crater-like’ behaviour can be explained with the help of fig. 24 where
the small decrease of T, in the interval of the existence of the tetragonal
phase is actually caused by spontaneous deformations. At the same time
there are no serious reasons to expect that the electron motion along chains
can be described in the tight-binding approximation which would be the
necessary condition for the well pronounced peak at E = -2T’. In $ 4 we
have already revised our previous point of view concerning this question
(Gor’kov and Dorokhov 1976a).
We have made the peak structure (32’) one of the centres of attention in
our review. One of the reasons for this, as was mentioned, consists in the
existence of the ‘precursor’ temperature behaviour of the magnetic suscep-
tibility for most of the A-15compounds. The fine structure in the density of
states due to impurities, briefly described at the end of the preceding section,
obscures the question to some extent.
It has been shown above that the existence of the logarithmic peak could
be an additional mechanism for the martensitic transformation in Nb,Sn
and V3Si because it brings the fast temperature dependences of the electronic
contribution into the elastic moduli. Formulas of $ 5 5 and 6 have only a
qualitative character since such essential features as, for example, the
dependence of the effective electron-phonon interaction on temperature (see
fig. 13b), coupling between various order parameters etc. have not been
considered. Moreover, the logarithmic peak (32’) can be considerably
weakened by the factor (2/n2)c. Nevertheless, the results concerning the
dependence of T, on strains, the higher sensitivity of T,,, to various factors
and, in particular, the enhancement of values of the critical magnetic fields
(see eqs. (82), (84)) are in correspondence with experiment and can be there-
fore considered as a manifestation of the peak-like singularity.
As a whole the theoreticalpicture described above looks quite self-consistent.
The crucialexperimentto test the basic idea concerningthe one-dimensionality
of the transition atom chains could be the investigation of the temperature
CH.7, 8 8) PROPERTIES OF A-15 COMPOUNDS 587

behaviour of the phonon modes with wave vectors in the [l 111 direction. If it
happens that the softening of the phonon spectrum abruptly disappears when
the wave vector goes out of the plane (110) it would be strong evidence in
favour of the picture suggested above.
A very serious difficulty for the further development of theory and its
comparison with experiment is the lack of experimental data extending over
the whole set of physical parameters and obtained from one and the same
single crystal with a well-defined composition. Some other methods of
composition control independent of the resistance ratio measurements are
desirable. Investigation of the magnetic susceptibility behaviour as a function
of composition could provide very important information concerning the
electronic density of states. Probably the study of Nb3Sn could be preferable
since in this compound the temperature interval between T, and T,is large
enough to investigate its electronic properties without additional complica-
tions connected with superconductivity.
Many A-15 compounds like, for instance, V3Ga show a considerable
increase of the magnetic susceptibility on cooling, Ascribing this fact to the
fine structure in the density of states it is reasonable to expect according to
the foregoing, some manifestation of the peak (32’) in the structural para-
meters. Certainly, the structural transition by itself could be absent since this
is only a question of the magnitude of the interaction constant d , , on the
one hand, and of the peak location on the other. (We have also mentioned
that impurities smooth the peak (32’) out due to scattering effects.) Neverthe-
less, a more careful study of structural properties (and in particular the
temperature behaviour of the moduli) for single crystals of these com-
pounds would be interesting. If the peak position corresponds to a rather
large distance from the stoichiometric composition or if the peak is smoothed
out the structural parameters (elastic constants) can still have some anomalies
in their temperature behaviour. This is possible if the three-dimensional
character of the spectra does not eliminate completely the initial instability
of the one-dimensional approximation (some effects of the order of
(T/T*)’). We have pointed out this possibility in $j 3. Perhaps this is just the
case for Nb,Al where some small temperature variation of the sound
velocities has been observed at almost constant magnetic susceptibility.
[See also the corresponding results for V,Ge (Testardi 1973).]
In conclusion we shall mention a certain incompleteness of the theory.
Everywhere, beginning with the question about the singularities in the
density of states and ending with the results of $j 6* concerning the super-
*These results are obtained in Gor’kov and Dorokhov (1976b).
588 L.P. GOR'KOV

conducting properties, the structure of the electronic spectrum has been

considered in the absence of electron4ectron and electron-phonon inter-
actions. The importance of interactions in the formation of the band structure
and in enhancement of the paramagnetic susceptibility is well known [see
the review paper (Gladstone et al. 1969)l. In the estimate of v(0)for Nb,Sn
and V,Si obtained from the magnetic susceptibility the large values of v(0)
also attract some attention. In 9 3 it has been shown that in our quasi-one-
dimensional model for the properties of A-15 compounds interactions play
an even more important role. Unfortunately any three-dimensionalapproach
like the random phase approximation is not applicable here even qualitatively
since the three-dimensionality parameter is supposed to be small (T* < AE).
It would be very interesting to investigate (even numerically and in an over-
simplified model) the mutual influence of the scattering processes [eqs. (21'),
(21")] and of the tunnelling between chains and, in particular, their role in
restoring the Fermi liquid concept of quasiparticles at sufficiently low
temperatures.
In the foregoing we have noted several times that due to the large number
of possible parameters it seems preferable to compare the theory with
experiment at the current level of the latter using a more phenomenological
picture. This approach has been suggested recently by Bhatta and McMillan
(1976). They have used the ideas described above concerning the electronic
nature of the structural order parameters and written down the Landau-
Devonshire expansion for the free energy of these compounds. Their general
conclusion is that on this basis it is possible to get excellent agreement with
the existing experimental data. A vulnerable point of their theory was the
neglect of the temperature variation of the magnetic susceptibility.

AcknowIedgements

The author would like to thank O.N. Dorokhov for essential assistance in
the preparation of the manuscript and A.F. Dite for much editorial advice.

References
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Axe, J.D. and G. S h e , 1973, Phys. Rev. B8,1965.
BarisiE, S. and P. DeGennes, 1968, Solid State Corn. 6,281.
Batterman, B.W. and C.S. Barrett, 1966, Phys. Rev. 149,296.
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Berthel, K.H., D. Eckert and A. Handstein, 1975, 4th Int. Symp. Reinstoffe in Wis-
senschaft and Technik Dresden.
Bhatt, R.N. and W.L. McMillan, 1976, Phys. Rev. B14,1007.
Bychkov, Yu.A.,L.P. Gor’kov,I.E. Dzyaloshinskyi, 1966,ZhETP50,738.
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Dzyaloshinskyi, I.E. andA.1. Larkin, 1971,ZhETP61,791.
Gladstone, G., M.A. Jensen and J.P. Schrieffer, 1969, in: Superconductivity,ed. R.D.
Parks (Marcel Dekker, New York).
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Gor’kov, L.P. and O.N. Dorokhov, 1976b, Solid State Comm. (in press).
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Horovitz, B., H. Guttreund and M. Weger, 1975, Phys. Rev. B12,3174.
Hulm, J.K. and K.D. Blaugher. 1974, Low Temperature Physics-LTI3, eds. K.D. Timmer-
haus, W.J. OSullivan and E.F. Hammel (New York).
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Kurmaev, E.Z. and S.A. Nemnonov, 1971. Phys. StatusSolidi (b), 43,K49.
Mailfert,R.,B.W. Battermanand J.J. Hanak, 1967, Phys. Lett. MA,315.
Maita, J.P. andE. Bucker, 1972, Phys. Rev. Lett.29,931.
Matheiss, L.F., 1975,Phys. Rev. B12,2161.
Menyhard, N. and J. S6lyom, 1973,J. Low Temp, Phys. 12,529.
Moskalenko,V.A. and L.Z. Kon, 1966,ZhETP 50,724.
Pokrovskii,V.L., 1961,ZhETP40,641.
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Shirane,G. and J.D. Axe, 1971, Phys. Rev. B4,2957.
Shirane, G., J.D. Axe and R.J. Birgeneau, 1971,Solid State Comm. 9,397.
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This Page Intentionally Left Blank
 CHAPTER 8

LOW TEMPERATURE PROPERTIES OF

KONDO ALLOYS
BY

G. GRUNER and A. ZAWADOWSKI

Central Research Institute for Physics, Budapest, Hungary

Progress in Low Temperature Physics, Volume VIIB

Edited by D.F. Brewer
Q North-Holland Publishing Company, 1978
Contents

1 . Introduction 593
2. Basicmodels 595
3. The Kondo effect 604
3.1. Experimental evidence for the magnetic-nonmagnetic transition 605
3.2. Theory of the Kondo e!€ect above TK 610
4. Properties below the Kondo temperature 615
4.1. Wilson’s numerical solution and Fermi liquid theories 615
4.2. Experimental results for T Q TIC 629
5. Phenomenologicalapproaches to the general case 638
6. Conclusions 644
Note added in proof 645
Referenoes 645
1. Introduction

Sincethe early days of metal physics it has been a well established experimental
fact that some impurities with an unfilled 3d shell have well-defined magnetic
moments when dissolved in simple metals, such as copper, whereas others
are nonmagnetic. A striking phenomenon, the resistance minimum, was also
discovered more than forty years ago, and its connection with the magnetic
impurities has been emphasized. The systematic study of dilute alloys of 3d
elements in simple hosts however, started only around the 'Fifties, when the
consequences of magnetic moments in metals became clarified by experiments
which measure local properties of alloys. Magnetic and nonmagneticimpurity
states were first accounted for by Friedel and Anderson; the Hartree-Fock
solution of the proposed model led to a clear distinction between the magnetic
and nonmagnetic states. The explanation of the resistance minimum by
Kondo in 1964 started an enormous activity in this field. The resistance
minimum signals the onset of a smooth transition to a nonmagnetic state at
low temperatures; subsequent experimental and theoretical efforts con-
centrated on the nature and details of this transition. Properties well below
the characteristic temperature, called the Kondo temperature TK,were
firmly established only later, and simple power laws of temperature found
by very careful experiments are now interpreted by a Fermi liquid theory.
The renormalization group treatment of the models accounts properly for
the relationship between this low temperature state and the high temperature
behaviour.
Experiments on a wide range of alloys demonstrate a common behaviour,
with characteristic temperatures ranging from the mK region to above room
temperature. The temperature dependence of the impurity resistivity Rimpand
of the susceptibilityXimp characteristic of a typical Kondo alloy are schemati-
cally plotted in fig. 1. At high temperatures Ximp exhibits a Curie-Weiss
behaviour, whereas Rlmpapproaches a constant value which can be accounted
for by the Hartree-Fock (HF) treatment of models discussed in 52. The
logarithmic increase of Rimpwith decreasing temperature is due to the non-
perturbative nature of the problem, and was first discussed by Kondo. The
flattening off both of the resistivity and of the susceptibility at lower tern-
594 G. GRUNER AND A. ZAWADOWSKI [CH. 8, J 1

peratures is associated with the disappearance of the effective moment of

the impurity - as evidenced also by specific heat experiments. The basic
features of the transition to a nonmagnetic ground state, summarized in 0 3
are well accounted for by theories which start from the high temperature,
weak coupling limit; they are however insufEcient to describe the properties
at T Q TK.The resistivity saturates at zero temperature and is determined
by the charge neutrality of the singlet ground state. Near to T = 0 the
properties are similar to those of a Fermi gas. Fermi liquid theory works well
in this region; this, and evidence for the internal structure of the singlet
state will be discussed in 54, together with the relationship between the

sirrplepowcr crossover region logarithmic r q o n

Llaw region
~ 1 -_
T
Fig. 1. Schematic temperature dependence of the impurity resistivity R,, and inverse
impurity susceptibility~,,,,,-l.Characteristic temperature dependences and various regions
are indicated in the w e .

low and high temperature properties, established by Wilson by numerical

calculation. Phenomenological approaches which endeavour to account for
general features for arbitrary alloy systems will also be discussed in this
section.
Since this paper focuses only on the basic developments in this field it is
by no means exhaustive. Details and elaborated discussions of various
properties can be found in several reviews. The experimental situation has
been discussed by Van den Berg in Volume IV of this series (Van den Berg
1964). This was followed by the review of Kondo (1969) and that of Heeger
(1969). The theoretical and experimental developments are summarized in
CH.8, 0 21 PROPERTIES OF KONDO ALLOYS 595

Magnetism V (1973) and in the review papers of Rizzuto (1974), Griiner

and Zawadowski (1974).

2. Basic models

The static magnetic susceptibility associated with the 3d atoms dissolved

in simple metals is generally used to establish the magnetic character of the
impurities. Various impurities in different hosts display widely different
properties. Manganese has a well-defined magnetic moment in copper; at
low impurity concentrations, where magnetic interactions between the
impurities are absent, the susceptibility is given by

where 8 is negligibly small, peff 5pB close to that corresponding to s = $,

N

the free spin of manganese. Chromium and iron also possess a magnetic
moment in copper, but 8 is larger; in the case of nickel impurities however
only weak Pauli paramagnetism is observed. Vanadium and cobalt are
borderline cases; for these impurities 8 is of the order of room temperature.
The situation is rather similar in a gold matrix, but in aluminium neither of
the 3d impurities shows clear-cut magnetic behaviour (Rizzuto 1974).
The appearance of a magnetic moment at the impurity site thus depends
both on the host matrix and on the 3d element. In a free 3d atom Coulomb
and exchange forces are responsible for the magnetic moment. The admixture
of the 3d wave functions with the conduction electron band of the host leads,
however, to delocalization of the impurity electron states, and, in case of
strong admixture, to the destruction of interactions which favour magnetic
behaviour. These ideas were first applied by Friedel (1956) to account for
magnetic and nonmagnetic impurities. The model Hamiltonian applied by
Anderson (1961) leads to results in the HF treatment which are closely
analogous to those derived by Friedel using scattering theory. In the so-called
non-degenerateAnderson model orbital degeneracyofthe d states is neglected,
and the impurity is represented by a localized orbital at energy ed. The
Coulomb interaction is given by the term Undgd-o where n d o = ad&,# + *is
the occupation number of the d level for spin o and U is the Coulomb
coupling. The admixture of the d-level with the conduction band states is
represented by a vkd transition matrix element. The Hamiltonian operator of
596 G. GRUNER AND A. ZAWADOWSKI [CH. 8, $ 2

the model is given by

where the first term represents the host states, with u& and aka the creation
and destruction operators of the conduction electrons.
The mixing of the d and s states leads to a broadening of the d-level.
Via the ‘golden rule’ one obtains

where I Vl is the appropriate average of vkd, and P,,(&~)is the density of host
states at the Fermi level for one spin direction. The density of d-states has a
Lorentzian form

(2.4)

and the occupation number

With Coulomb interaction absent the position of the d-leveland the occupation
number are the same for’o and -cr and the impurity is obviously non-
magnetic. In the HF approximation the Coulomb interaction is taken into
account by an effective field, which shifts the position of the d-level, and

The shape of the resonance is, however, unchanged. Equation (2.6) together
with (2.5) leads to two coupled equations
CH.8, § 21 PROPERTIES OF KONDO ALLOYS 597

Depending on U, A and on &d one obtains one solution, for which (n,,) =
(nd-,), or two symmetrical solutions with (&) # (nd-,). The former
corresponds to the nonmagnetic, the latter to the magnetic impurity. The
phase boundary separating the two solutions is given by

that is the usual Stoner condition for magnetism in metals. The system is
magnetic if UPd(&F)> 1, which occurs for large density of d-states at the
Fermi level. From eq. (2.4) it follows that magnetism is favourable if the
d-states are half filled and in this case the condition reads U/nA = 1. For
less or more than half filled d-states, the condition for the appearance of
magnetic moment requires larger U or smaller A.
When the orbital degeneracy of the d-states is also included, the intra-
atomic exchange 9 between the different orbitals m also appears, and the
number of d-electrons ranges from 0 to 2(21+ 1) = 10. The Hamiltonian for
orbital degeneracy is given by

where only terms containing occupation numbers have been retained. The
HF treatment leads to the condition for the appearance of spin magnetism
(Blandin 1967)

(v+21F)pd(EF) = 1. (2.10)

An orbital magnetic moment can also develop in the degenerate case, the
condition for this being given by

-- -
For 3d elements in a metallic host U 3 eV and .F 0.5 eV are the
generally accepted values, for noble metals A 0.5 is obtained from various
estimations (Griiner 1974). Thus ( U + 4 9 ) / n A 3 and the magnetic be-
N

haviour of manganese impurities, where N = 5 and the d-level is half filled

in noble metals is explained. Chromium and iron have nearly half filled
598 G. GRUNER AND A. ZAWADOWSKI [CH.8, $ 2

d-levels and are also magnetic; at the end of the series the nearly filled d-level
-=
of nickel leads to small Pd(&F), and so (U+49)PQ(&F) 1. Indeed, nickel is
nonmagnetic in noble metals. Aluminium has a larger host density of states,
and so A is larger; early estimates led to A 2 eV (Friedel 1956). With this
N

value even for the half filled d-level the condition for magnetism is never
reached, thereby explaining the nonmagnetic behaviour of 3d impurities in
an aluminium matrix. With the above values of U,9 and A it is apparent,
that the condition (2.11) is rarely fulfilled and so the orbital moment is
generally quenched. The HF analysis of the degenerate Anderson model
leads to the condition for spin magnetism which is determined by the joint
effect of Coulomb and exchange forces. This may be an artifact of the HF
approximation, and will be discussed later. It is however useful to analyze
the various experimental quantities by replacing U by U + 4 9 and then
using the results obtained for the nondegenerate case. In the following
therefore U + 4 9 will be called U unless stated otherwise.
The best confirmation of the Friedel-Anderson picture comes from optical
and photoemission experiments. Detailed measurements on a wide range of
alloys are available, these also give accurate experimental values for the basic
parameters involved. In accordance with the suggestion of the model, two

-
optical absorption peaks were observed in AgMn, one below, one above
the Fermi level. A 0.5 eV and from the poxion of the absorption peaks
one arrives at U 5 eV (Myers et al. 1968), in agreement with the theoretical
N

estimates. Contrary to this, only one absorption peak was found in CuNi,
with A = 0.3 eV and Ed = -0.75 eV (Drew and Doezema 1972). ByTnte-
grating the density of states up to E~ the number of electrons on the d-level
is 8.9, in excellent agreement with the number of d-electrons of the nickel
atom N = 9. The positions of the d-resonances in AgMn and CuNi obtained
by optical experiments are shown in fig. 2. In s p z of consixrable efforts
no clear-cut experiments are available in aluminium-based alloys.
The HF solution of the Anderson model can be related to the phase shift
formalism used by Friedel (1956). The phase shifts qu(w) of the scattered
conduction electrons are given, for angular momentum 1 = 2, by

where ( n u ) is the occupation number of the d orbital for spin Q. This relation
also follows from the Friedel sum rule
(2.13)
CH.8, 8 21 PROPERTIES OF KONDO ALLOYS 599

if the nonresonant qo and q l , etc. phase shifts are neglected, and only the
resonant q2 phase shift is considered. N is the total number of d-electrons
of the impurity and N = (21+ l)C,(n,) expresses the charge neutrality.
The formalism is particularly useful to express various physical quantities
in terms of phase shifts, as only the values of phase shifts at the Fermi level
appear in the macroscopic parameters.

Fig. 2. Position of the d-resonances in &Mn and @Ni obtained by optical experiments.
The parameters of the Anderson model appropriate for the two alloys are also given.

Thus, keeping only the 1 = 2 phase shift, the impurity resistivity is given by

+
Rfmp= Ro5(sin2~,(eF) sin2q-,(EF)), (2.14)

with q,(eF) = (n,)n. For magnetic impurities, <nu) # (n-,) and therefore
by filling the impurity d-level progressively two maxima are expected, and
are also found at room temperature in copper and gold matrices - see fig. 3 -
where impurities are magnetic in the middle of the series. In contrast to this
in an aluminium matrix, only one peak is found (fig. 4). This has been taken
as evidence for the nonmagnetic behaviour of the impurities in this matrix.
A local property, the charge perturbation around the impurities, has the well-
known form
 0. GRUNER A N D A. ZAWADOWSKI [CH.8, 8 2

Au host

0 Cu host

10 "

5 '*

4-
Ti V Cr Mn Fe Co NI

Fig. 3. Impurity resistivities in copper and gold at room temperature.

7 ~

5T
4 -I
i

3-

*I I
11
1
j .
TI
~ I
V
t
Cr Mn
I--+
Fe
-+---------t-----
Co NI
+-
Cu
a
Zn

Fig. 4. Impurity resistivities in aluminium at room temperature.

CH. 8, $ 2 PROPERTIES OF KONDO ALLOYS 601

at large distances r from the impurities. This perturbation can be measured

by nuclear quadrupole effect experiments, which give essentially the same
general picture as that obtained from the resistivity. The amplitude of the
perturbation (Blandin 1967) is

A = 5(sin q,(eF)+sin q - , ( ~ ~ ) ) , (2.16)

and displays the same characteristics as those shown in figs. 3 and 4.

The magnetic moment of the impurity is given by the difference of occu-
pation numbers for D and - D electrons. In terms of phase shifts

Equations (2.14) and (2.17) can be used to construct appropriate phase

shifts the significance of which will be discussed later. When the impurities
are magnetic, a spin perturbation develops around the impurity moments.
In terms of the H F analysis, this is given by the difference of the charge
perturbations for opposite spin electrons. In particular in the strongly

-
magnetic limit when one resonance is well below, the other well above the
Fermi energy, sinq,(EF) q,(eF) and sinq-,(E,) = n-q,(eF) and so

= (2/npO(EF))[q~(eF)-(n- ~ C ( ~ F ) )cos
I (%Fr)lr3* (2.18)

In this strongly magnetic limit the magnetic moment of the impurity is

only slightly modified by the interaction with the conduction electrons [see
eq. (2.17)], and then it is appropriate to represent the impurity by a well-
defined spin. The Hamiltonian of this so-called s-d model is given by

H = -2 j Y C ( ~ ) Sd3r,
-~(~) (2.19)

where 9 ( r ) is the distance dependent s-d coupling constant, S the impurity

and 9 the conduction electron spin. When the s-d coupling is weak, per-
turbation theory can be applied to calculate various physical quantities. The
impurity resistivity can be obtained using the ‘golden rule’. Both spin-flip
and non spin-flip scattering contributes to the scattering amplitude, and the
resistivity is given by

Rimp= 5 R 0 ~ 2 & , p ( ~ i m1)

p+ (2.20)

with S ( k ) taken to be constant. One-third of the resistivity comes from spin

conserving, two-thirds from spin-flip scattering.
602 G . GRUNER AND A. ZAWADOWSKI [CH.8, 0 2

The interaction between the impurity spin and conduction electrons leads
to an antiferromagnetic polarization of the host states, and the effective spin
is reduced. This reduction is proportional to .F in the first order of per-
turbation,

This polarization, however, is not homogeneous, but decays as r - j with

increasing distance r. The perturbation called the RKKY perturbation was
first derived by Rudermann and Kittel (1954), by Kasuya (1956), and by
Yoshida (1957); it has the form

h ( r ) = (Ftp0(~F)/87t)cos (2kFr)/r3. (2.22)

A more elaborate analysis in the framework of the Anderson model shows

that this reduction appears rather on the d-level than in the conduction
band (see e.g. Zawadowski and Griiner 1974).
Looking at expressions (2.22) and (2.18) and at (2.21) and (2.17) it is
clear that the Anderson model in the strongly magnetic limit and the s-d
model lead to similar expressions for the various physical quantities, but with
parameters of the particular models. The comparison of relevant formulae
can, in fact, be used to derive the correspondence of the parameters of the
two models. This correspondence, was, however, derived by Schrieffer and
Wolff (1966) using a canonical transformation. When U and &d are much
larger than A, the Anderson model reduces to the s-d model, with

(2.23)

When Ed is below the Fermi level, and Eda+ U above, F is negative. With

obtains F&) -
parameters, appropriate for CuMn, i.e. U = 5 eV and A = 0.5 eV one
0.05 eV. T h z the weak coupling limit is appropriate.
Strictly speaking equation (2.23) is not appropriate for cases where the d-level
is not half filled, as then, due to the charge neutrality, Edu A. Neverthe-
N

less, F is expected to increase by going away from the symmetric case,

N = 5.
9 can, in fact, be measured very accurately by the nuclear magnetic
resonance (NMR) method. The RKKY spin perturbation, eq. (2.22), gives
rise to a distribution of hyperfine field shifts at the host nuclear sites and
leads to a broadening of the host NMR line. This has been widely used to
CH.8, 8 21 PROPERTIES OF KONDO ALLOYS 603

determine 9,and the observed values are collected in fig. 5 for noble metal
hosts. 9 has a minimum in the middle of the series and increases with
increasing or decreasing N,which can be taken as a direct consequence of
the Schrieffer-Wolff transformation, given by eq. (2.23).

'ti- ,___-L_I_-.I---I-
V Cr Mn Fe Nt

Fig. 5. s-d couplings in noble metal hosts, derived from NMR experiments ( M i m o 1971).

The HF solution of the Anderson model can also be used to account for
other parameters, such as thermoelectric power and specific heat. In both
cases the width of the d-resonances appears: the electronic specific heat
coefficient is given by

(2.24)

and the thermoelectric power reads

s = n(ki/3e)(T/A)(sin 2qu(eF)+ sin 2q-#(&F)). (2.25)

With parameters such as resistivity or effective magnetic moment taken

from other experiments, reasonable values for the density of states or for
the width A are obtained in cases where the impurity is strongly magnetic
or weakly magnetic. Discrepancies have however been found for alloys
which are near to the magnetiononmagnetic boundary. AuV or CuCo have
already been mentioned as borderline cases, and -AlMnTso fallsinto this
604 G. GRUNER AND A. ZAWADOWSKI [CH.8, 3

category (Griiner 1974). Here the analysis of y and Sleads to a large density of
states at cF and so to a narrow effective width of the d-states suggesting that
the HF approximation breaks down in these cases.
Indeed one does not expect a sharp boundary between magnetic and non-
magnetic impurities suggested by the HF approximation; due to the low
dimensionality of the problem, fluctuations are expected to smear out the
sharp phase transition between the magnetic and nonmagnetic limit. This
transition moreover, occurs also when the temperature is changed; the
impurity which has a well-defined magnetic character at high temperatures
may display properties characteristic of nonmagnetic impurities below
certain temperatures. The transition as a function of temperature is smooth,
but leads to drastic temperature dependences of various physical properties.

3. The Kondo effect

The first evidence for strongly temperature dependent effects in dilute alloys
came from resistivity experiments in the early ’Thirties. In cases when the
impurity is magnetic, the resistivity starts to rise at low temperatures, which,
together with the phonon resistivity, yields a resistance minimum. Sub-
tracting the phonon part, the impurity resistivity was shown to obey the
empirical law

Rimp N log T+const. (3.1)

The explanation of this logarithmic temperature dependence is due to Kondo

(1964), who in the framework of the s-d model showed that in third order of
perturbation the scattering amplitude of the conduction electrons diverges
as T -,0. The first Born approximation leads to the temperature independent
term given by eq. (2.20). In the next order, depending on the intermediate
state, both the direct and the exchange scattering are operative. For the
direct scattering the electron with momentum k is scattered from the initial
state to the intermediate state with k“ and is then scattered to the final
state k‘. In the exchange process an electron-hole pair is created first, then
the hole annihilates the electron with momentum k. In both cases the
scattering rates contain the term

where f k is the Fermi distribution function. The spin-flip scattering gives

CH.8, Q 31 PROPERTIES OF KONDO ALLOYS 605

S’S- for the direct and S-S+ for the exchange process, and thus the total
scattering amplitude is proportional to

The spin conserving scattering rates proportional to S‘ do not contribute to

this term. The integral diverges for T -t 0 or for w + 0. Taking the simple
form for the density of host states

-D<&<D
PO(&) = (3.4)
0 otherwise

one obtains a logarithmic temperature dependence, and the resistivity is

given by

Rimp= Ro4FZS(S+1)[1 +49p0(eF) In k T / D ] . (3.5)

The logarithmic behaviour of the resistivity is in accordance with the experi-

mental observations, and is the consequence of the Fermi statistics of the
conduction electrons and of the commutation rules for the spin operators.
The impurity spin represents an internal degree of freedom, which provides
an indirect coupling between electrons scattered successively on the impurity
spin. The situation is reminiscent of superconductivity where the phonon
operators provide the effective coupling between the conduction electron
states.

3.1. EXPERIMENTAL
EVIDENCE FOR THE MAGNETIC-NONMAGNETIC TRANSITION

A diverging scattering amplitude at T = 0 is clearly not a final solution but

merely signals the breakdown of perturbation theory. Subsequent theoretical
efforts concentrated on better solutions of the problem. Experimentally, the
nature of the anomalies and, in particular, the low temperature properties
have been studied intensively on a wide range of appropriate alloy systems.
The anomaly in the behaviour of the resistivity was found to be accompanied
by anomalies in the thermoelectric power and specific heat and these were
shown to be the consequence of a smooth transition to a nonmagnetic
impurity state, as evidenced by the magnetic susceptibility.
The finite Weiss constant 8 is a property of single impurities and is not due
to interaction effects. 8 can, in fact, be taken as evidencefor the disappearance
606 G . GRuNJ3R AND A. ZAWADOWSKI [CH. 8, 8 3

of the effective spin at low enough temperatures. Allowing perfto be tem-

perature dependent, the susceptibility is written as

A Curie-Weiss form, and thus a finite susceptibility a t zero temperature

suggests a disappearing effective moment as T --t 0. This was first demon-
strated by Van Dam et al. (1972) on AuV; the temperature dependent
effective moment in this alloy is s h o w n 3 fig. 6. Magnetic susceptibility
experiments measure the z-component of the magnetization, thus the above

50 100 150 200 250 300

T [OK]

Fig. 6. Temperature dependenteffective moment in AuV alloys, derived from the magnetic
susceptibility.

experiment demonstrates that (S') = 0 a t T = 0. The nonmagnetic nature

of the impurities is further demonstrated by the temperature dependence of
the impurity specific heat. Careful experiments, performed by Triplett and
Philipps (1971) in CuCr alloys are shown in fig. 7. A broad anomaly is
observed at temperatures around 8, and the area under the anomaly leads to
the entropy

AS= C,(T)/TdT = R In (2S+ 1) (3.7)

with S = 3, which is the high temperature spin of chromium impurities in

copper. The impurity spin has therefore been removed from the system a t
low temperatures, and the total spin of the impurity conduction electron
system is zero at T = 0.
CH.8, Q 31 PROPERTIES OF KONDO ALLOYS 607

The logarithmic increase of the resistivity provided early evidence for

anomalous transport properties. Subsequent experiments demonstrated that
this phenomenon is related to the smooth magnetic-nonmagnetic transition
detected by susceptibility and specific heat experiments. Following the
logarithmic behaviour at high temperatures, the resistivity flattens off some-
what below 8 and saturates well below this temperature. Evaluation of Rlmp
is particularly difficult due to phonon effectsand deviationsfrom Mathiessen's
rule. However, by changing the host properties, e.g. by alloying, various parts

- 5 1 at pprn 0 0-0,.

A33.6 pprn A A S
IY 021.2 ppm
A
"pa
2.0 A
U

0 .

I o 'A l
0.1 1:o tb
T [OK]

Fig. 7. Impurity specific heat as a function of temperature in S C r alloys (Triplett and

Philipps 1971).

of the resistivity curve can be investigated. Figure 8 gives a summary of such

studies for -Cu
x- Au, -,Fe alloys, with characteristic temperatures, called TK,
also indicated. The Kondo temperatures obtained by fitting the experimental
points to a calculated curve, given by eq. (3.14), with TKas a free parameter.
The thermoelectric power shows a broad hump around 8 giving further
evidence for a strongly energy and/or temperature dependent scattering
amplitude. This parameter is also strongly iduenced by the background
potential scattering, and direct comparison with theoretical expressions is
difficult; it can however be used to evaluate the characteristic temperature
of the magnetiononmagnetic transition.
608 G . GRUNER AND A. ZAWADOWSKI [CA.8, 8 3

The above examples were taken from alloy systems, where the transition
from the high temperature magnetic behaviour to the nonmagnetic low
temperature state occurs at low temperatures. It is emphasized that alloys
viewed traditionally as 'nonmagnetic' can also retain magnetic properties at
high temperatures. Early indications for this in the case of AlMn alloys
(Caplin and Rizzuto 1967) have been followed by careful susceptibility
r f
+ .-, - . f -. . , ----.--

Cu -0.01 at % Fe 24 6

at% Fe13
C ~ o A u , o - O O Oat% Fe 8 6
4 Au -0.0025 at% Fe 0 24

0 +------t----t- f
, ~ f .
T/T~
+.- -

0.01 01 10 10 100

Fig. 8. Impurity resistivity versus temperature in Cu,Aul -xFealloys (Loram et al. 1970).

experiments in this system, and indeed the high temperature behaviour

of ximp(T)can be described by a Curie-Weiss law with 8 somewhat above
room temperature (Miljak and Cooper 1976). In addition to this the impurity
resistivity of A1 3d alloys at high temperatures display a behaviour rather
similar to t h a t found in copper alloys as shown in fig. 3, suggesting that
at least in the middle of the series 3d transition metal impurities develop a
magnetic moment above room temperature (Kedves et al. 1973).
CH.8, 8 31 PROPERTIES OF KONDO ALLOYS 609

The characteristic temperatures where the magnetic-nonmagnetic transi-

tion occurs thus span a wide range, from well below 1 K to the lo3 K region.
The characteristic temperature is not well-defined as various physical
quantities are smooth functions of temperature. Rough estimates can be
obtained on purely experimental grounds, leading to Kondo temperatures
depending on the parameter measured. For the susceptibility 0 is usually
taken as TK, for the resistivity the temperature where Rlmprises to half of
the T = 0 value, for the specific heat and thermoelectric power, the tem-
perature where the maxima are found. Also, comparisons of the measured
temperature dependences with theoretical expressions containing TK as a
free parameter can be used to evaluate the Kondo temperature.
TK values for gold, copper and aluminium alloys are collected in fig. 9
(for details of evaluation of TK see Griiner 1974). The wide range of Kondo

-
I
CuMn

-
AuMn

TI V Cr Mn Fe Co Ni

Fig. 9. Kondo temperatures of 3d transition metal impurities in gold, copper and

aluminium.
610 G. GRUNER AND A. ZAWADOWSKI [CH. 8, 0 3

temperatures, when correlated with changes of the basic parameter of the

Anderson and s-d models, suggests a non-analytic dependence of TK on
these parameters. Comparing the overall behaviour of TK with 9 inferred
from NMR experiments and shown in fig. 5, an exponential relation

appears to hold, where TFis the Fermi temperature; ambiguities in 9 and

TK do not allow the exact proportionality and the pre-exponential factors to
be determined. F is given by the parameters of the Anderson model, and it is
evident from eq. (2.23) that TK depends in a nonanalytical way on the

CuMn, TK - -
strength of the Coulomb interaction and on the position of the single particle
resonances. In the symmetrical case, for U/nA 3 which is appropriate to
K. For U/nA 1, the case of AlMn, TK lo3 K.
N -
Also, when U is the same, but Ed,,is near to the Fermi leFl, TK is higher. It is
evident from fig. 9 that alloys which are clearly in the nonmagnetic limit of the
Anderson model can also be incorporated into the general picture-with
kTK of the order of the single particle width A. Thus, the Kondo effect is
not a purely low temperature phenomenon, and is characteristic in general of
dilute alloys. Properties below the Kondo temperature TK, analyzed in
detail in $4, supply additional evidence for this, and point to a unified
behaviour in the function of TIT,.

OF THE KONDO EFFECT ABOVE TK

3.2. THEORY

The first improvement of Kondo’s result came from calculations of further

terms of the perturbation series. The first correction to the resistivity given
by eq. (3.5) or to the scattering amplitude is proportional to fln(kT/D) or
9ln(w/D), where w is the energy which becomes large as Tor o goes to zero.
Thus it is better to organize the perturbation result for any correction term
according to the coupling 9 and to the logarithm in the following scheme

a, +u,F In ( k T / D ) + u z F Inz ( k T / D )+. ..

+b 1 9 +bzF2In ( k T / D )+ ...
+c l F +c z F In (kT/D)+ ...
+ .... (3.9)
CH. 8, 31 PROPERTIES OF KONDO ALLOYS 611

If the logarithmic terms are large one may keep the first line and drop the
others (logarithmic approximation). The leading logarithmic terms were
first summed by Abrikosov (1965). This approximation leads to spurious
divergency due to the appearance of the term

[1 - 2 F p 0 In (kT/D)]-’ (3.10)

in the scattering amplitude which diverges for $r < 0 at

Tg = D exp (+ 1/2Fp0) (3.1 1)

called the Kondo temperature. This divergency cannot be physical as no

real phase transition is expected and is due to the following two limitations
of the leading logarithmic approximation:

(i) the result is always real, as the imaginary parts contribute to the next
approximation ( b i ,c i , ... may be complex), thus the analytical properties
of these results are wrong;

(ii) only those diagrams give contributions to the scattering amplitude

which may be cut into pieces by cutting only one electron line and one spin
line in each step (‘parquet’ diagrams).

Further attempts set out to avoid at least one of these two restrictions.
Enormous mathematical efforts have been made to drop the first restriction
thereby keeping ‘parquet’diagrams but retaining correct analytical behaviour.
The solution was manifested in the Nagaoka-Suhl integral equations for the
spin conserving (t) and spin dependent ( 2 ) part of the scattering amplitude

T = t+ra.S (3.12)

which has been derived by various methods. These methods, Nagaoka’s

decoupling scheme (Nagaoka 1965) for the Green’s function equation,
Suhl’s equation (Suhl 1965) derived on the basis of Chew-Low scattering
equations and the summation of the ‘parquet’ diagrams (see e.g. Brenig and
Gotze 1968) are essentially equivalent. These equations have been solved
exactly and compared with experiments. The prediction was a logarithmic
temperature dependence for different quantities (resistivity, susceptibility,
etc.) both at high and at low temperatures.
612 G. GRI)NER AND A. ZAWADOWSKI [CH. 8 , 8 3

According to Hamann's solution (Hamann 1967) the spinconserving

part of the scattering amplitude exhibits a peak around w = 0,

t(w+ie) = (1/2ip0){l-In (w/g)[ln2(T/g)+S(S+ 1 ) ~ ~ - ~ / ' }(3.13a)

while the spin-flip part has a maximum around

t ( w ) = (1/2po)[ln2(w/T:)+S(S+ 1)n2]-'l2 (3.13b)

for T = 0. Similar formulae are valid for w = 0, but for T = 0 only w needs
to be replaced by kT under the logarithms.
The resonance formed symmetrically around w = 0 is called the
Abrikosov-Suhl resonance. Similar solutions have been obtained by others
(e.g. Brenig and Gotze 1968, Zittartz and Miiller-Hartmann 1968).
The resistivity increases with decreasing temperature (Hamann 1968) and
has the form

= 1-In ( T / ~ ) [ l n 2 ( T / T+S(S+
Rimp(T)/Rimp(0) ~) (3.14)
The heat capacity exhibits a peak around T = +e(Bloomfield and Hamann
1967), while the magnetic susceptibility is

(3.15)

for lnT/Tf 1. A decrease in the effective moment by lowering the tem-

perature is the consequence of a correlation between the spin polarization
of the conduction electron gas and the impurity spin, i.e. the impurity spin
is gradually screened by the conduction electrons (Miiller-Hartmann 1969).
The above expressions of the various physical quantities are in fair agree-
ment with experiments at temperatures T > TK but this agreement breaks
down progressively with decreasing temperatures. This is demonstrated in
fig. 8, where the observed temperature dependence of the impurity resistivity
is fitted to eq. (3.14). The fit is appropriate in the high temperature region
but the theoretical curve deviates sharply at low temperatures. In the
temperature region T < TZ the calculated resistivity is logarithmic while
experimentally a simple power law behaviour is observed. A similar dis-
crepancy was found for other quantities, with the low temperature logarithmic
behaviour predicted being found to disagree with experimentally observed
power dependences.
CH. 8 , 0 31 PROPERTIES OF KONDO ALLOYS 613

This disagreement between theory and experiment initiated another line

of approximations, in which the effect of a large number of electron-hole
pairs was included. It was noted first by Anderson in a series of papers
(Anderson 1967a, b, 1970, 1972; Anderson et al. 1970; Yuval and Anderson
1970) that the Kondo effect is a typical example of infrared divergency,
because the energy spectrum of the electron-hole pairs created by the spin-flip
processes does not contain a gap.
As a next step Anderson and Yuval(l971) noted that the spin-flip process
in the Kondo problem can be regarded as a sudden change in the spin
dependent mean field potential acting on the electrons and caused by the
rigid impurity spin. The time dependence of this potential acting on, e.g.
the spin up electron is shown on fig. 10, where the sudden changes represent

Fig. 10. Time dependence of the impurity potential acting on a spin-up electron.

the spin-flips. Thus, the Kondo effect can be regarded as a series of subsequent
X-ray absorption problems which have been solved exactly in the large time
limit. Anderson and his co-workers tried to solve the problem by combining
this idea with scaling. However, as the strength of the spin-flip processes
increases as a result of scaling the time differences between spin-flip pro-
cesses liecome shorter, thus the asymptotic solution breaks down.
Anderson (1970) also called attention to the scaling properties of the
problem, characteristic of situations where the infrared divergencies dominate
the dynamical behaviour. Such scaling was first discussed by Anderson (1970),
and by Anderson et al. (1970). It was simplified considerably by Anderson
(1970) using the ‘poor man’s’ method. S6lyom and Zawadowski (1974)
slightly modified this method to make it capable of accounting for higher
order corrections.
If, for example, the one particle scattering amplitude T‘ is kept invariant
under the scaling, and the cut-off D is changed by AD and the coupling 9
J
614 0.GRUNER AND A. ZAWADOWSKI [CH.8, g 3

by A.F, then the compensation can be formulated as

(aT’/aD)AD+(aT’/aF)AF= 0. (3.16)

To have a definite scaling formula the coefficients aT‘/aD and aT’1a.F

must be known. However these can be calculated only by using perturbation
theory. If these calculations are performed up to third order the scaling
equation has the following form

(3.17)

Tp’ T
Fig. 11. Solution of eq. (3.13, F e a ( T )= *(a = kT)keeping the first (1st) and fist
two (2nd) terms in the bracket of eq. (3.17). The dotted line represents the expected exact
result.

This scaling agrees with those obtained by more sophisticated renormaliza-

tion group calculations by Abrikosov and Migdal (1970) and by Fowler
and Zawadowski (1971) where the Gell-Mann and Low version of the
renormalization group known from field theory has been applied, The first
order scaling, when only the second order term is retained on the right-hand
side of eq. (3.17), leads to a solution which contains the factor given in eq.
(3.10), thus it diverges at o T i similarly to Abrikosov’s original solution.
N

The solution of the differential equation given in eq. (3.17) is shown in fig.
11, with initial parameters o = D and P = So;the scaled value is called
.Feff. At small D this solution saturates at Saff = 1, called the fixed point.
The fixed point occurs in the intermediate coupling region where it is not
sufficient to keep only the first terms in the perturbation series. The fixed
point therefore may be spurious, nevertheless eq. (3.17) leads to a crossover
CH.8, 8 41 PROPERTIES OF KONDO ALLOYS 615

temperature between the weak and strong coupling regions, given by

TK = D(21Flp0)1’2exp (1/29tp0). (3.18)

The appearance of the factor (2191p0)1/2indicates a slight modification from

the previous expression of the Kondo temperature given by eq. (3.11).
Sakurai and Yoshimori (1973) were able to show that the binding energy of
the singlet state is also proportional to TK given by eq. (3.18).
The above theoretical treatments clearly demonstrate that the Kondo
temperature represents a crossover between the weak coupling and strong
coupling limits.
Starting from the high temperature region all the known analytical methods
break down near TK. The reason for this is the lack of typical dominating
diagrams in the strong coupling region, thus the full series on the right-hand
side of eq. (3.17) must be evaluated. The exact scaling curve is therefore not
known, but Anderson (1972) and Fowler (1972) argued, on the basis of
dimensionality, that the scaling curve must go to infinity in the way indicated
in fig. 11, because no singularity is expected at finite 9. The trajectory,
however, cannot be determined by the methods summarized before.
We note finally that all the results obtained in the weak coupling region
have also been derived by constructing a trial wave function for the ground
state (for a review see Yosida and Yoshimori 1973).

4. Properties below the Kondo temperature

In the low temperature region, at temperatures well below TK the strong

coupling between the impurity and the conduction electrons leads to proper-
ties drastically different from those observed above and around the Kondo
temperature. Recent theoretical predictions valid in the T 4 TK region
are verified by findings arrived at by very careful experiments performed
in the last couple of years. We review first the theoretical achievements and
then the experiments will be analyzed in the light of available theoretical
results.

NUMERICAL SOLUTION AND FERMI

4.1. WILSON’S LIQUID THEORIES

The theoretical treatment of the Kondo Hamiltonian, discussed in 5 3, acted

as a bottleneck for some time until Wilson dropped completely the analytical
approach and produced a numerical solution. The solution is a perfect
616 G. GRUNER AND A. ZAWADOWSKI [CH. 8, 8 4

combination of the use of a computer to diagonalize a Hamiltonian and of

the renormalization group concept and is valid in the whole temperature
range including the spin compensated state at very low temperatures, the
paramagnetic behaviour at high temperatures and the crossover region. The
method was first applied to the Kondo Hamiltonian and was extended to the
Anderson model later.
After Wilson's solution, many of his low temperature results were derived
in other ways. In the framework of the Kondo Hamiltonian, Nozieres (1974)
was the first to suggest a simple, phenomenological Fermi liquid theory. In
the Anderson model the behaviour of a Fermi liquid type had already been
demonstrated in the late 'Sixties and by combining these results an almost
exact description has been obtained for T = 0 (see e.g. 43.5 in Gruner and
Zawadowski 1974). Further developments are due to Yosida and Yamada
(Yosida and Yamada 1970, 1975; Yamada 1975a' b), who treated the com-
plete perturbation series for the symmetric Anderson model.

4.1 . I . Wilson's numerical solution of the s-d model

Theories discussed in the previous section demonstrate that the summation
of a certain class of diagrams cannot give a final solution of the Kondo
problem around and below the Kondo temperature. On the other hand,
different scaling approaches strongly indicate the existence of scaling, thus a
renormalization group method appears to be an adequate approach even if
the original Gell-Mann and Low version fails. Wilson developed a new
formulation of the renormalization group theory which does not rely on
perturbation theory nor on diagrammatic calculations. The advantage of the
method is a general procedure for reducing the degrees of freedom and for
finding the new Hamiltonian by computer. In the present problem the
computer is used to diagonalize Hamiltonians, and naturally the number
of states cannot exceed a few hundreds. Considering the impurity and a few
one-electron states of the conduction band the total number of the combined
states is especially large due to the spin variable. As the Kondo problem is
associated with the region of the Fermi level Wilson used the following
scheme. First, he considered a couple of conduction electron states and the
impurity and diagonalized the Hamiltonian. Next he included one more
one-electron state from the low energy region near to the Fermi level, and to
keep the total number of the st,ates constant before diagonalizing the
Hamiltonian he dropped the states with highest energies. The procedure
turned out to be adequate to find the character of low-lying excited states,
and the temperature dependences of the various physical quantities.
CH.8, 8 41 PROPERTIES OF KONDO ALLOYS 617

At first the Kondo problem was transformed to a form suitable for scaling.
The original model with uniform energy distribution for the conduction
electrons was not adequate. Consequently Wilson introduced a model
Hamiltonian with discrete energy levels proportional to *A" where A is
an arbitrary constant in the range of two and n is an integer. In this model
there are only a few states in the cut-off region, but the density of states is
infinite at the Fermi level. The model is given by the Hamiltonian

H = 1n-"(u:u,,-b,+b,)-~(A+uA).S
n
(4.1)

where a,, and b, are annihilation operators for electrons above and below
the Fermi energy, S is the operator for the impurity spin, u is the Pauli
operator. The operator A, defined as A = CP,oA-"'2(a,+b,,), is introduced
to represent the exchange interaction. It replaces the electron field operator
on the impurity site $(O) appearing in the s-d interaction $'(O)a$(O). The
modification in A by the factor is necessary to compensate for the
effect of the increasing number of electrons around the Fermi energy in order
to keep the rate of the spin-flip processes invariant.
This Harniltonian is transformed into a hopping Hamiltonian of a semi-
infinite one-dimensional hopping chain by a canonical transformation.
The impurity is coupled to the end of the chain to site 0, and the Hamiltonian
has the form

whereS, is the electron annihilation operator on site n and it is, furthermore,

a linear combination of different a, and b, operators. The hopping matrix
elements vary along the chain and E, -+ 1 as n -ia.Let us denote by HN
the Harniltonian obtained from that given by eq. (4.2) by cutting the upper
limit of the summation at n = N. The procedure of increasing the number
of states is given by going from HNto HN+1.The recursion form is

Wilson first diagonalizes IfN in some approximation then in the numerical

approximation he drops all the states of H N except for the first 100 to 300
eigenstates before introducing H N + + .
The essence of the calculation is to show that a spin-compensated state is
formed in the original model. This can be done by proving that the impurity
61 8 G. GRUNER AND A. ZAWADOWSKI [CH. 8, $ 4

spin is infinitely strongly coupled to the single electron at site n = 0 to form a

spin singlet. The only effect of the presence of the singlet on the other electrons
is that a weak interaction is induced between electrons on the first neigh-
bouring sites next to site n = 0. The computer calculation is designed as
follows.
At the beginning it is assumed that the exchange is very weak, thus the
electron gas on the hopping chain is almost free. By carrying out many steps
of the renormalization group procedure the spin compensated state is found,
where the singlet is formed at the end of the chain, and thus the site n = 0
can be dropped, because an infinitely large energy is necessary to polarize
this singlet. What remains is the weakly interacting chain but starting with
site n = 1. Thus it must be shown that the treatment of the interaction must
actually result in losing site n = 0.
In order to signal this transition one should look for the energy spectrum
of the lowest-lying states without interaction. The situation is somewhat
different depending on whether the number of sites is even or odd. The
energy levels of the noninteracting system in rescaled energy units for even
and odd N values are

Wad, 0.6555 1.976 4 8

1.297 2.827 442.

Let us assume that we start with a weak coupling problem with N even,
N can then be increased step by step all the time by one. In every second step
an energy spectrum is recovered which is similar to the original one until
at around N = 20 a systematic strong change occurs and in the further steps
the spectrum tends to converge into a spectrum characteristic of odd N.
The change of the first excitation energy is shown in fig. 12. Thus, one electron
tied together with the impurity spin is gradually decoupled from the chain,
and the infinitely strong binding energy indicates an effective new exchange
coupling Feff = 00.
The success of Wilson’s theory is that it can be applied to calculate the
susceptibility and heat capacity. If the new excitation spectrum is known
these quantities can be evaluated by computer. It should be mentioned that
the low temperature calculations can be simplified if the excitation spectrum
obtained by computer is fitted to the spectrum of a model problem in which
a weak pseudopotential with two adjustable parameters is acting on sites
n = 1 and 2. By the appropriate choice of these parameters a fairly large
CH.8, 8 41 PROPERTIES OF KONDO ALLOYS 619

number of excitation energies are described with excellent accuracy. We

restrict ourselves only to the final results and for mathematical details we
refer to the original paper (Wilson 1975).

I
06

+ ++
t
+
+
0.11
I
-t +t +
N
*
U 18 22 24 28

Fig. 12. The behaviour of the first excitation energy in Wilson's solution.

O
b 1 2 3 4
f
Pig. 13. Temperature dependence of the magnetic susceptibility of the s-d model
(Wilson 1973).

The susceptibility multiplied by temperature Tximpis a universal function

of TIT, and does not depend directly on the bare exchange coupling as was
suggested by Anderson and his co-workers (Yuval and Anderson 1970;
Anderson et al. 1970). The impurity susceptibility is shown in fig. 13. The
Kondo temperature TK has been determined numerically and the best
analytical fit for its dependence on the bare coupling was obtained by the
620 G. G R m E R A N D A. ZAWADOWSKI [CH.8, 8 4

following mathematical expression

TK & F ~ ~ O ) ( ~ ~ F I ~P O
X ){P -” ~1/2191~0+
13312F~01
+O(S2p;)}
(4.4)
where E(.Fpo) is a regular function of J representing the cut-off. The non-
analytical part of this formula agrees with the form obtained from the
analytical renormalization group calculation [see eq. (3.18)] ; however the
exponent contains some polynomial which can be neglected in the very weak
coupling limit. The susceptibility for T < T K approaches a constant,

thus the ground state is a singlet. For T > TK,a Curie-Weiss behaviour is
found which can be very accurately fitted by the formula

Finally, the ratio of the coefficient of the linear term in the specific heat and
of the susceptibility can be very well fitted by

This formula can also be derived by analytical methods and will be discussed
in the next subsections.
The calculations have been extended by Krishnamurthy et al. (1975) to
the symmetric Anderson model with one localized impurity orbital. The
result for the parameter value 8A/nU = 0.064 is shown in fig. 14 where the
dotted line represents the computer result for the s-d model with an adjusted
Kondo temperature

exp{l/2po@ef,+ ..-1,
TK(d, W = (1/12)u[l +f(p0P,ff)I(2po~ect)”~
(4.8)
N

where 2po.Feff = -8A/nU andf@,.@’,,,) is a smooth function. Thus the

expression for the Kondo temperature agrees with the previous result with
geff determined on the basis of the Schrieffer-Wolff transformation [see
eq. (2.23)]. The numerical results show that the mapping of the two problems
on each other is very accurate, exceeding all expectations. It is pointed out
that the effective bandwidth &U[l +f(pPCrf)] before the expression (4.6) is
CH.8, 4 41 PROPERTIES OF KONDO ALLOYS 621

proportional to U ; this may be explained by the fact that according to the

Schrieffer-Wolff transformation the approximation #eff = const. is correct
only in the energy range characterized by U and perf gradually going to
zero beyond this range. Calculations have been performed for the non-
magnetic limit aA/U 1 as well, and the susceptibility obtained can be
expressed by

as was to be expected on basis of the analytical calculation (e.g. Menyhhrd

1973; Yamada 1975a).

Fig. 14. Temperature dependence of the magnetic susceptibility of the Anderson model
(Krishnamurthy et al. 1975).

For more details we refer to Wilson’s original work (Wilson 1975) and to a
brief discussion by Nozitres (1975).

4.1.2. Noziires’ Fermi liquid theory

Wilson’s numerical solution (Wilson 1973, 1975) proved that a singlet
ground state is formed at T = 0. The polarization of the conduction electrons
is described by the ground state of the hopping model. This state has a very
complicated structure in terms of the unperturbed states because in each
diagonalization more and more electron-hole pairs are mixed in. Using the
fact that the spectrum of the excited states is very like the free electron
spectrum, Nozibres has proposed a Fermi liquid picture. The theory is
formulated in the framework of the scattering theory and uses phase shifts.
622 G. G R m R A N D A . ZAWADOWSKI [CH. 8, 9 4

The essence of Wilson's numerical solution is built in the theory in the form
of the following assumptions:

(i) The elastic scattering is spin-conserving. The spin-flip process breaks up

the ground state and as in this spectrum a threshold is expected at an energy
around kT,, the amplitude of these processes must show a strong exponential
decay as T = 0 is approached.
(ii) The elastic scattering can be described by a phase shift q&) fully deter-
mined by the occupation numbers of the single electron states, and deviations
from the ground state values are given as a function of energy E

(4.10)

where $,JE) = 9" +(ao')V(~); this assumption is characteristic of Landau's

Fermi liquid theory. The phase shift can be expressed by the magnetization
of the conduction electrons nt -nl = rn as

If,(&) = q o + u E + a p n y (4.11)

where a is defined by the following expansion

$(&) = qo+u&. (4.12)

In this way the impurity specific heat Cimpand the magnetic susceptibility
ximpdue to the impurity can be easily expressed
CimplC = UhPOY (4.13)
and
Xtotal = x + Ximp = x[1 + a l v o +24"hl, (4.14)
where C is the specific heat of the conduction band, and x = 2p0(gp0)2 is
the Pauli term. Thus

(4.15)
CH.8, 8 41 PROPERTIES OF KONDO ALLOYS 623

Furthermore, it is shown that if the Kondo resonance is tied to the Fermi

level, a simultaneous shift in E and p (the chemical potential) by the same
amount leaves the phase shift invariant, thus

a+2p0$' = 0. (4.16)

A further assumption made on the basis of Wilson's numerical result is that

I+Ttl e I$Tll and so
$"$" = 0. (4.17)

The last two equations combined with eq. (4.15) give

(4.18)

in agreement with eq. (4.7).

(iii) In order to calculate the electrical resistivity it is assumed that at T = 0

the phase shift ~(0)= 3.
The first term of the temperature dependence of the resistivity comes from
the energy dependence of the phase shift, thus after taking the thermal
average over 6n one gets

(iv) The inelastic scattering near to T = 0 is dominated by the creation of

one electron-hole pair, which can be given by a scattering amplitude depend-
ing only on the spin variables. Thus, depending on whether the two electrons
have parallel or antiparallel spin this amplitude is A,, or A + + respectively.
From simple phase space arguments it follows that the inelastic scattering
is proportional to T2.Thus the total conductivity is

(4.19)

Considering a very weak electron-electron interaction the electron+lectron

scattering amplitude has already appeared in terms of the phase shift on
Sn, thus
624 G . GRUNER AND A. ZAWADOWSKI [CH. 8, 8 4

From the previous assumption given by eq. (4.17)it follows that I A, I&
,
IA , I and thus eq. (4.19)has the simpler form
p (10+nZTZaZ
~ imp (T)/~ im= ) = 1 + Tzn4p$(Cimp/C)*, (4.20)
where in the second form, a is expressed by the coefficient of the specific heat.

solution one must assume that @' -

In order to bring these results into agreement with Wilson's numerical
l/kT,. A more precise comparison can
be made by correlating the two forms for the susceptibilities given by eqs.
(4.5)and (4.14); this gives
TKa = 0.324. (4.21)
We emphasize that the theory is valid for S = 3: generalizations for
arbitrary spin have not been performed yet.

4.1.3. Anderson model at T = 0

In the Anderson model the only interaction involving the s-electrons is the
s-d mixing. The effect of s-electrons can therefore be incorporated exactly
into the width of the d-electrons, thus only the Coulomb interaction acting
between electrons on the d-levels is left for further treatment. Schrieffer and
Mattis (1965)showed that the problem of d-electrons is essentially equivalent
to a many-body problem of an energy band with band shape similar to a d-level
and with Coulomb interaction between the electrons. It differs, however, from
band magnetism, as the momentum conservation characteristic to a real band
does not enter. The effect of the Coulomb interaction is smooth a t U = 0 and
no singular behaviour isexpected. (In the Kondo model the singular behaviour
in the exchange interaction can be characterized by the non-analytical
expression exp($.Fpo), but in the Anderson model it becomes analytical as
exp { - U/nA} if U and J are connected by the Schrieffer-Wolff transforma-
tion.)
It has been shown using phase space arguments similar to Landau's Fermi
liquid theory that the imaginary part of the self-energy correction &(w)
due to the Coulomb interaction disappears at the Fermi level. This observa-
tion permitted Langreth (1966) to conclude that at the Fermi level the
scattering of the conduction electrons on the d-level is elastic, thus at w = 0
the scattering amplitude can be exactly expressed by a phase shift given as

(4.22)
CH.8, 8 41 PROPERTIES OF KONDO ALLOYS 625

This connection gradually breaks down as 101 increases because ImC does
not remain negligible. Furthermore, Anderson and McMillan (1967) and
Langer and Ambegaokar (1961) showed that the Friedel sum rule holds
exactly at T = 0, thus the charge of the impurity ion can be given by the
phase shifts qlms(m = 0) as

(4.23)

where 1, m,0 are the orbital and spin quantum numbers. In the case of
impurities with an open 3d shell the dominant contribution comes from the
1 = 2 scattering channel, so in the first approximation v ~ , , , , ,for ~ 1# 2
can be neglected. In the absence of a magnetic field a singlet ground state is
expected - in agreement with the experimental result discussed previously;
thus q l = 2 , m , ashould be independent of rn and 0. Keeping only the dominant
1 = 2 phase shift in the Friedel sum rule and assuming that the impurity is
completely screened (charge neutrality) at T = 0, the phase shift at the
Fermi level is determined as

ql=2(0 = 0) = nN/lO, (4.24)

so the forward scattering amplitude is

fkk(W = O+iS) = (5/npo)exp {i(nN/lO)}sin nN/lO. (4.25)

This simple and - in the dominant phase shift approximation - exact result
has several important consequences. It leads to the resistivity formula given
by eq. (5.1) and to the amplitude of the Friedel charge oscillation in the
asymptotic, large distance region. As the scattering amplitude is simply
related to the d-electron Green’s function Yd,

For T = 0, the density of states at the Fermi level pd(w = 0) is also deter-
mined by the charge neutrality and by singlet behaviour of the ground
state. It is obvious that the high temperature density of states must be
roughly Hartree-Fock in character, thus in the case of magnetic impurity, it
must exhibit two peaks representing the two d-levels. As has been emphasized
by Griiner and Zawadowski (1972), this high temperature result is expected
to be correct on a large energy scale since strong distortion in the density of
626 G. GRuNER AND A. ZAWADOWSKI [CH. 8, g 4
states would lead to a larger change in the d-electron energy than the energy
associated with the temperature range discussed. Therefore, only one
possibility remains for explaining the large d-electron density of states at
w = 0, namely, to assume a narrow resonance around the Fermi level whose
height is determined by the phase shift at T = 0 and washed out at high
temperature. Further discussion of this point is left to $ 5 .

4.1.4. Fermi liquid theory for the Anderson model

From the previous discussion it is obvious that a Fermi liquid theory can be
applied to the d-electrons even for finite Coulomb interaction. Summation
of a certain class of diagrams is, however, not sufficient (Tche and Zawadowski
1972; MenyhCrd 1972, 1973). Recently, Yosida and Yamada have published
a series of papers (Yosida and Yamada 1970, 1975; Yamada 1975a, b) in
which a perturbation expansion has been given for the symmetric non-
degenerate Anderson model in a closed mathematical form with the aid of
determinants built up from the unperturbed Green’s function. The success
of this method is due to the fact that it is not restricted to summation of a
certain class of diagrams, and therefore this method is capable of determining
general relations between different quantities.
The main point is that the coefficients of the power expansion of different
quantities such as free energy, susceptibility, self-energy are given in terms of
determinants like

0 B12 %13 ... 91,

9 2 , 0 ... ...
D”(1, ..., n) =
... (4.27)
...
...
YnI 9112 ... 0

where Q,, is the unperturbed Green’s function

$i, = - (T,{adu(ti>adu(z,)}), (4.28)

with w, = (n/b)(2n+ 1). Similar determinants have already been used by

Yuval and Anderson (1970). As was first noticed by MenyhCrd (1973) not
only the free energy but also the even and odd parts of the static impurity
susceptibility can be expressed by these determinants
CH.8, 8 41 PROPERTIES OF KONDO ALLOYS 627

(4.29)

x [D2"+2(1,2, . . . I 2n+2)D2"(ly2, ... 2n)]con,

and

x [Dz"+z(l,2, ..., 2n+2)02"+2(2,3, ..., 2n+3)],,n, (4.30)

and the subscript 'con' means that only those products which correspond to
connected diagrams should be retained. Yosida and Yamada could express
all the different physical quantities by fey,. and i d d . Comparison of the free
energy and susceptibility at low temperature shows that the heat capacity
Cimp= yT for low temperature is determined completely by Ti,, as

Thus from eqs. (4.29) and (4.31) it follows that

In the large U/nA limit, where the s-d Hamiltonian can be applied, j&, =
jiodd (see Yamada 1975a), and so

This result is different from that obtained in the U = 0 limit where jiodd = 0,
thus the interaction produces a universal enhancement by a factor two.
This result was also derived by Anderson and Armytage (Armytage 1974)
by scaling the problem to an exactly soluble limit (Toulouse limit, see also
Rivier 1976). The first manifestation of this result, was, however, given by
Wilson's numerical solution, which was followed by Nozi6res' Fermi liquid
theory. The one-particle d-electron Green's function is given as

(4.34)
628 G. GRUNER AND A. ZAWADOWSKI [CH.8, 8 4

with
c(0)=
d
-W(jeven- 1)-i~d~~dd[(XZ~Z/d2)+(WZ/Az)]. (4.35)

Thus the self-energy shows the character of Fermi liquid theory and I m x d
contains the contribution of the creation of an electron-hole pair, as well.
The resistivity can be also obtained
(4.36)
By comparisori of these results with those valid for the s-d model -where
the only characteristic energy is the Kondo temperature TK- one finds that
xevenand Xodd take over the role of the Kondo temperature for large U, so that
kTK A/x"even A/l?odd- (4.37)

Yamada (1975a) following Menyhhrd's work (1973) calculated many

-
quantities up to the fourth order of perturbation theory. The convergence is
surprisingly good even, for instance, for U/nA 2. The d-electron density of
states obtained in second order of perturbation theory indicates a HF-like
d-resonance and the central peak called the Abrikosov-Suhl resonance (see
fig. 15). This will be discussed in Q 5.
A comparison of these theoretical results with experiments ought to provide
important information for the internal structure of the resonance and the
validity of strong or weak correlation limits for various alloys. This is,
however, not the case, and the reason is that orbital degeneracy may strongly

Fig. IS. Density of states obtained from perturbation treatment of the Anderson model
(Yamada 1975a).
CH.8, 841 PROPERTIES OF KONDO ALLOYS 629

influence the above results. The Anderson model has been generalized for the
orbital degenerate case and the consequences of the model have been worked
out by Yoshimori (1976) using a technique based on Ward identities. The
basic difficulty, however, is connected with the appropriate form of the
generalized Anderson model.
To discuss orbital degeneracy, Anderson (1961) suggested a two-level
model which was designed for the HF approximation. Therefore, the inter-
action on the d-level was expressed in terms of occupation number operators.
This restricted Hamiltonian has been generalized in several steps (for
references, see $2.2 of the review by Griiner and Zawadowski 1974) to re-
establish correct symmetry properties, but the matrix elements with four
different quantum numbers have been neglected. In general, the Coulomb
interaction in second quantized form must be written as

(4.38)

where the summation on the quantum numbers is restricted only by the

conservation law m +m' = A +A'. Thus, to get correct results for orbital
degeneracy, one should start with a Hamiltonian containing all terms, and
the matrix elements (mm'l f i ' f i ) must be parametrized taking into account
the symmetry of the d-orbitals by using the results known from atomic
physics. Such a theory probably contains more than three Fermi liquid
parameters and it is expected to give relations between various physical
quantities different from those arrived at by using the restricted form of the
Anderson model.

4.2. EXPERIMENTAL
RESULTS FOR T 4 T K

In spite of intensive efforts, the low temperature transport, magnetic and

thermal properties of various alloys have only recently been clarified.
Experimental evidence available at present suggests that different alloys
ranging from the nonmagnetic limit of the Anderson model to the strongly
magnetic limit display basically the same behaviour as a function of the
reduced temperature T/T,. At low temperatures the temperature dependences
are completely different from that found at temperatures above TKand are
also in disagreement with those suggested by theories briefly summarized
in $ 3 . Besides the investigation of the temperature dependences of the
macroscopic quantities, long-range correlation effects, implied by the non-
630 G. GRUNER AND A. ZAWADOWSKI [CH.8. 8 4

perturbative aspect of the problem, have also been sought but have not yet
been explored in full detail.

4.2.1. Temperature dependence of the macroscopic parameters

Experimental work on various dilute alloys demonstrates that the logarithmic
temperature dependences observed at temperatures T > TK are modified,
and at temperatures well below the Kondo temperature analytical dependences
on the temperature are observed. Experimental work in this temperature range
is particularly difficult due mainly to interaction effects between the impurities.
In some cases single impurity effects can be masked by interactions even for
concentrations as low as 100 ppm.
Simple power law behaviour in the Kondo-region was first observed by
Caplin and Rizzuto (1967) in AlMn,- where the impurity resistivity has the
form

Rimp(T) = R,rnp(O)[I -(T/edzI, (4.39)

with OR = 530f30 K. The characteristic temperature when interpreted in

terms of an energy dependent scattering potential gave a width significantly
smaller than the single particle width A. This temperature dependence was
related to the specific heat and susceptibility. Subsequent experiments on
.-CuFe demonstrated that this is also the case for this alloy (Star 1971) and
that non-analytical behaviour, in apparent agreement with early theories,
is due to impurity interaction effects. This is demonstrated in fig. 16, where
Rimpis plotted for low and high impurity concentrations (Star 1969). The
T 2 temperature dependence, found also in other systems, suggests a Fermi
liquid behaviour, with characteristic temperatures close to TK values given
in fig. 9. This conclusion is reinforced by the behaviour of the thermo-
electric power which is a linear function of temperature in the low tem-
perature region. The specific heat can also be interpreted in terms of Fermi
liquid theory: in alloys ranging from - CuCr to - AlCr cimpis proportional to
the temperature.
The magnetic susceptibility which exhibits a Curie-Weiss behaviour at
temperature T > T, saturates at low temperatures and the leading tem-
perature dependence is given by

~imp(T) Ximp(0)tl -(T/81>21

=I (4.40)

for -
CuFe, with 8, similar to that found for the resistivity. The change-over
CH.8, 8 41 PROPERTIES OF KONDO ALLOYS 631

from the Curie-Weiss behaviour is particularly important as this parameter

has also been evaluated theoretically. The temperature dependence of the
impurity susceptibility (Alloul 1976) is shown in fig. 17, the insert demon-
strating the low temperature behaviour given by eq. (4.40). The data were
obtained by Mossbauer and NMR techniques, and they are in broad agree-
ment with susceptibilitydata obtained by macroscopic experiments (Tholence
and Tournier 1970), but allow a more accurate evaluation of the temperature
dependence. The significance of the agreement between macroscopic and local
experiments will be discussed later.

0.52 6

0.524

0.522

Fig. 16. Temperature dependence of the impurity resistivity in G F e alloys of various

impurity concentrations (Star 1969). The logarithmic expression is derived on the basis of
theory described in 9 3.

The various macroscopic parameters are thus determined by simple power

dependences on the temperature. This has been used by experimentalists to
argue that, as a consequence of the Kondo effect, a simple, Lorentzian
resonance appears at the Fermi level. The various thermal, magnetic and
transport properties follow immediately from such an assumption, the pre-
diction of which agrees with those made by the HF approximation to the
Anderson model in the U + 0 limit.
632 G. GRUNER AND A. ZAWADOWSKI [CH. 8, fi 4

Recent theories of the s-d model and the Anderson model in the strong
correlation limit also lead to Fermi liquid behaviour but with relations
between the various quantities somewhat different from those given by the
simple resonance model.

-u
45

AK
-
K
-12

-10

-8

4
0 10 LO 30
j:-0.2

-2

J
0

Fig. 17. Temperature dependence of the impurity susceptibility in G F e . Kd("Fe) refers

to the iron impurity hyperfine field shift, AK/K to the temperature dependence of the shift
at near neighbours of the impurity (Alloul 1976). The orbital contribution Korb has been
subtracted from the susceptibility.

The low temperature experimental data are in accordance with Fermi

liquid behaviour suggested both for the weak and strong correlation limit,
but strict comparison with theory is not possible at present. This is due to the
fact that only the non-degenerate Anderson model was considered, and this
is clearly inappropriate for 3d impurities.
Assuming that the scattering channels corresponding to different invalues
are independent, the various macroscopic parameters are multiplied by
CH.8, 5 41 PROPERTIES OF KONDO ALLOYS 633

21+ 1 ;in the following we use this factor to account for the low temperature
experimental results. This does not modify the relation between the various
parameters and leads to a relation Ximp/cimp the same as that obtained for the
non-degenerate case. It is, however, important when the characteristic energy
which determines the low temperature fluctuations is compared with TK,
the transition temperature.
Including the orbital degeneracy is this way, the assumption of a simple
Lorentzian resonance at the Fermi level, having a width A’ leads to

Rimp(T)= &,,(0)[1 -(T/8R)2] = Rjmp(0)[I - ( R ~ ~ ~ T ~ / ~ (4.41)

A ’ ~ ] ,
with the relations
2 2 2
Yimp/Ximp = (kB/h), YimpeR = 2(21+ 1)kB/‘d3* (4.42)

These agree with those obtained in the limit U + 0 by Yamada (1975a).

In the strong correlation limit U -, 00, in terms of a phenomenological
parameter ct introduced by Nozieres (1975) (but for 1 = 0)

Yimp = +&(21+ 1)~s Ximp = (4~b/n)(21+l)a,

R,,p(T) = R,mp(0)[1 -(T/8R)’] = Rimp[l -kZk2T2tlZ] (4.43)
and
YimplXimp = Bk2(kb/~3, YirnpeR = f(21+ 1)kB (4.44)
could be expected on the basis of a naive generalization. In table 1 the
specific heat, the zero temperature magnetic susceptibility and the co-
efficient of the T2 resistivity for CuFe, AuV and AlMn alloys are col-
lected, together with the phenomzologizl paramzers tl determined by
using eqs. (4.43). There is broad agreement between values determined from
different physical quantities, and a similar overall agreement can be achieved
using the simple resonance concept with A‘ defined in a phenomenological
way. The crucial difference between the two concepts is expected to show up
in the relation between the various parameters, shown in the last two columns
of table 1. It has been emphasized before, that predictions valid for the
orbital non-degenerate case have little relevance to the actual situation, and
therefore it is not possible to test their validity. We note only, that yimp81mp
is near to that predicted by the strong correlation case [see eq. (4.44)] while
634 0.GRUNER AND A. ZAWADOWSKI [CH. 8, 9 4

Table 1
Macroscopic parameters in the low temperature region for G F e , &V
and g M n . The phenomenological constants a-I were obtained from
eq. (4.43) where the subscripts refer to experiments from which a was
derived.

-
CuFe 800 4.9x 22 9 . 6 ~ 5= 48
&V 68 43 x 10-4 400 1 1 0 ~ 5 =550
YMn 44 23 x 10-4 630 206 x 5 = 1030

-
CuFe 2 1 x 5 = 110 69 0.75 -
17.6
8.2
= 2.0

24
&V 250x5 = 1250 1240 0.63 E~ = 2.9

27.7
-
AlMn 1950 1980 0.85 8 i 8= 3.3

- x ~for~ all~ three alloys, which is smaller by about a factor of 3

Y , ~ ~ / 0.7
than that predicted.
It must also be emphasized that both models assume that the only effect
concerning the various parameters is the appearance of a single, narrow
resonance at the Fermi level. This can be realized only for the symmetrical
Anderson model N = 5 , since in other cases the single particle resonances are
near to E~ and certainly have a strong influence.
Both a-' and A' are defined as phenomenological parameters, and both
are of the order of the Kondo temperature as determined from the high
temperature properties, or the temperature dependences around TK . Beside
this broad overall correlation it is of fundamental importance to establish
the proper relation between the characteristic energies which determine the
high energy T > TK and low energy T 4 TK properties. This relationship can,
in principle, be obtained by analyzing the high temperature experimental
data in terms of perturbation treatments of the s-d or Anderson model,
leading to T K as given by, for example eq. (4.4), and then correlating TK
with a as determined before. Another way to examine this relation is to
analyse experimental data in the whole temperature region from T > TKto
T < TKin the light of available theoretical results.
CH.8, 8 41 PROPERTIES OF KONDO ALLOYS 635

Only the magnetic susceptibility has been calculated over a wide tem-
perature range. xtmp(T)calculated from the s-d model and from the Anderson
model in the strongly magnetic limit are in good agreement, and are shown in
figs. 13 and 14, the zero temperature value being given by eq. (4.6). For the
CuFe alloy, on which the most detailed experimental data are available,
-
8 = 30 K (Tholence and Tournier 1970) and thus from eq. (4.6) TK = 15 K.
Extrapolating the Curie-Weiss relation eq. (4.6) to T = 0 leads to
ximp(T+ 0) = 0.O85g2&kTK, which is somewhat smaller than that evaluated
from eq. (4.5) in the T = 0 limit. Experimental evidence for this is supplied
by detailed susceptibility data on CuFe, presented in fig. 17, which indeed
strongly suggest that the Curie-Wzs fit extrapolates to lower values than
that actually measured at T near to zero. A computer fit of the experimental
data to the calculated temperature dependence has not been performed, but
nevertheless the above analysis strongly indicates that Wilson’s numerical
calculation represents well the experimental data in the whole temperature
region.
The transport properties have not been calculated in the crossover region,
and therefore no comparison with experiments is possible at present. The
evaluation of a is subject to ambiguity due to the orbital degeneracy, and
therefore the relation aT,, for which the theory predicts eq. (4.21) cannot be
established on experimental grounds.
It is evident nevertheless that the Fermi liquid properties predicted by
recent theories are well confirmed experimentally, and this is also the case
for the transition region as far as the magnetic susceptibility is concerned.
The orbital degeneracy appears to be an important factor, the role of which
should be clarified. Also the alloys investigated experimentally have less or
more than a half-filled d-shell, and this also appears to be important both at
low and high temperatures.

4.2.2. Correlationefects in the Kondo state

The appearance of the narrow resonance at the Fermi level and the many-
body screening aspect suggest that a coherence length
r= VFIkBTK, (4.45)

where vF is the Fermi velocity, has a fundamental importance at T 4 T K .

A naive approach to the problem would suggest that the coherence effect
appears in all physical quantities like charge perturbation, spin correlation
functions or spin polarizations (see 5 3). In that this has not been confirmed
636 G. G R m E R AND A. ZAWADOWSKI [CH.8, 8 4

by experiments, it supports the view that the Kondo effect is more compli-
cated than that of the appearance of a structureless resonance at cF.
The coherence effect for charge perturbation was first calculated by Mezei
and Griiner (1972), using a simple Lorentzian resonance for the scattering
amplitude. A strong depression of the oscillation amplitude A was found
<
for distances r < t where = v,/2r and r is the width of the resonance.
Nuclear quadrupole experiments performed on A1 3d transition metal alloys
indeed show a strong depression of the chargeperturbation in the case of
- AlSc and -
AlMn. In fig. 18 recent experimental data on - AlMn are reproduced.

q(
1

-
A l Mn

2c

10

1 2 3 4 5 6 7 8 9 shelln’
t t t
2.8 5.6 8.4 r(A)
Fig. 18. Experimental values of the electric field gradient around Sc and Mn impurities
in aluminium, The full curve is the envelope of the charge oscillation calculated from the
asymptotic expression, the dotted line is calculated by taking into account the pre-
asymptotic behaviour (Berthier and Minier 1973a, b).
CH. 8. $41 PROPERTIES OF KONDO ALLOYS 637

The full line is the asymptotic expression, given by eq. (2.15) with the
oscillations neglected.
The asymptotic form describes well the experimental points for non-
magnetic Sc impurities; for AlMn there is a clear depression of the charge
perturbation near to the impzities. Analysis in terms of the theory leads to
-
r 0.5 eV (see the dotted line in fig. 18). Thus r is definitely smaller than
the single particle width A and shows the importance of the many-body
resonance in the behaviour of the charge perturbation. r,on the other hand,
is larger than the width kT, obtained from the analysis of the macroscopic
properties of this alloy (see table 1); this may be due to the internal structure
of the resonance, or to the fact that both single particle and many-body
effects contribute to the depression of the charge perturbation. This is indeed
a possibility for AlMn which is near to the magnetienonmagnetic boundary,
and will be discussed later. Similar experiments have not been performed on
systems where the difference between kT, and A is larger; in CuFe or in
similar alloys this would enable a clear distinction to be made between the
effect of the two resonances.
In spite of considerable effort, the distance dependence of the spin correla-
tion functions of the type (S+ * a - ( r ) )has not been clarified experimentally.
Recent neutron experiments performed on CuFe are subject to ambiguities
due to large impurity concentrations used (c> 400 ppm); indeed, impurity-
impurity interactions have always played a significant role in this particular
system.
The spin polarization around impurities has been extensively studied by
NMR techniques. The host NMR is sensitive to spin polarization, which
gives rise to a broadening of the central line and also to the appearance of
distinct satellites due to the hyperfine interaction between spin density and
host nuclei. The line width is subject to impurity-impurity interactions, but
the satellite positions are independent of impurity concentrations and reflect
single impurity behaviour. The temperature dependences of satellite shifts in
Cu 3d transition metal alloys were first investigated by Boyce and Slichter
(1974) and later by Alloul(l976) in considerable detail. In CuFe a compari-
son of satellite shifts with the macroscopic susceptibility demonstrates
(Alloul 1976) that the perturbation is given by

Aa(r, T ) = A(T)B(r), (4.46)

where A has the same temperature dependence as zimp(T). The form of the
perturbation is thus not modified by the Kondo effect. The spin polarization
638 G. GRUNER A N D A. ZAWADOWSKI [CH. 8, !j 5

has no long-range nonperturbative part, it has the same form as that given
by the RKKY result [eq. (2.22)].In the HF analysis the spin perturbation is
given by the difference of the charge perturbations for spin-up and spin-
down conduction electrons to du(r, T ) = dp,(r, T)-dp-,(r, T ) [see eq.
(2. I5)] and therefore the behaviour of charge perturbation and spin polariza-
tion would be essentially similar. However, spin-flip scattering and the internal
structure of the resonance at eF strongly modify this result. The essential
point is that the charge perturbation reflects the properties of the bound
state, and the spin polarization that part which has been lifted by the external
magnetic field. No straightforward relationship is thus expected between
the two quantities. This has been borne out by the recent calculation of
Ishii (1976) who showed that in the Kondo state

(4.47)

where (S') represents the local spin polarization, at distances

D
kFrc < - In -. (4.48)
kDT.1 k TK

Thus da(r) is not modified at distances smaller than r compared with the
perturbative form. At distances r > r,

du(r, T ) = -(1/2n) (S') cos (2kFr)/r3. (4.49)

For CuFe, with D 10eV and TK 20 K, r,

N N - lo3 A, a distance well
beyond the experimentally accessible range. Thus, long-range nonperturba-
tive spin polarization is neither expected theoretically, nor observed experi-
mentally in dilute alloys in the Kondo state.

5. Phenomenological approachesto the general case

Theoretical solutions of the Anderson model and of the s-d model discussed
briefly in the previous section have been obtained for certain values of the
basic parameters which describe the impurity stdes in a metallic host. In
the weak correlation limit U -+ 0 the HF solution is appropriate for an
arbitrary hopping matrix element V,, and position of the d-level ed.
Correlation effects have only been treated in the symmetrical case, N = 5,
CH.8, 0 51 PROPERTIES OF KONDO ALLOYS 639

and in the limit U -, co : the s-d model is also appropriate only in this limit.
The basic concepts, the development of the singlet ground state, and long-
range correlation effects, as well as the crossover from the high temperature
weak coupling to the low temperature strong coupling limit are well under-
stood. Nevertheless, it is desirable to use these concepts, and the general
results obtained in the case of Anderson model, to describe the properties
of alloys (which do not fall within the limits where the exact solutions are
available), in a semi-empirical way.
Different phenomenological approaches are available. They are successful
in accounting for certain experimental quantities, including relationships
between them and also temperature dependences. They emphasize various
aspects of the problem and visualize the many-body effects in different ways.
Star (1969) postulated that a narrow Lorentzian resonance (with a width A')
develops at eF; the macroscopic, thermal and transport properties can then
be derived using standard formulae. Souletie (1972) and others (Loram et al.
1972; Nagasawa 1972), on the other hand, assumed that the magnetio
nonmagnetic transition can be described within the framework of the HF
solution with U 4 0 as T -P 0. A unified point of view has been presented
by Gruner and Zawadowski (1972). This approach incorporates both the
many-body and the single particle aspects of the dilute alloy problem.
Certain properties at T = 0 can be derived using the exact results valid
for arbitrary parameters of the Anderson model, in particular the scattering
amplitude, from which the resistivity can be evaluated.
Arguments given for the validity of the phase shift approach at cP (4 4.1)
lead to

Rimp(T= 0) = Ro sin2 (Nn/lO). (5.1)

It is essential to emphasize that this result, although having the same form
as that obtained from the HF solution in the nonmagnetic limit, is generally
valid for arbitrary strength of the Coulomb interaction. The T = 0 resis-
tivities, presented in fig. 19, can indeed be described by eq. (5.1) not on$
for aluminium-based, but also for copper- and gold-based alloys, in spite
of the double peaked structure shown in fig. 3 having been taken as evidence
for the magnetic behaviour in the last two cases. It is also important to
realize that the T = 0 resistivities reflect the scattering amplitude at ep,
and are independent of the structure of the resonance. Therefore the behaviour
displayed in fig. 19 cannot be taken as evidence for a Lorentzian resonance
with a single particle width A as suggested by the nonmagnetic HF solution;
640 G. GRUNER AND A. ZAWADOWSKI [CH.8, 8 5

Au k t
o Cu host

Ti V Cr Mn Fe Co NI Cu Zn

Fig. 19. R,,, versus the 3d atomic number in the T + 0 limit for Cu, Au and Al based
alloys (Gruner and Zawadowski 1972).

with t(eF) determined by the charge neutrality, and different assumptions

can be made concerning the energy and temperature dependences.

5.1. NARROW
RESONANCE LEVEL CONCEPT

Star (1969) who first showed experimentally that the temperature depen-
dences of the various macroscopic parameters are determined by simple
power laws in CuFe, postulated that a simple resonance width of the order of
kT, appears atthe Fermi level. The scattering amplitude has the form

t(o) - 1/(d +Ar2). (5.2)

The resonance itself has no temperature dependence, but thermal smearing

results in strong temperature dependences a t temperatures kT A'. At N

low temperatures the Bethe-Sommerfeld expansion gives eqs. (4.41)and (4.42)

and analysis of various thermal, magnetic and transport properties leads to
the values close to a-' given in table 1. At higher temperatures the calculated
behaviour faithfully describes the overall temperature dependences obtained
experimentally and shown in figs 6, 7 and 8.
Clearly, the Abrikosov-Suhl resonance provides the theoretical back-
ground of this phenomenological description which has been proved to be
CH.8, 8 51 PROPERTIES OF KONDO ALLOYS 641

extremely useful for relating various physical quantities. The simple form of
the resonance excludes, however, the possibility of logarithmic behaviour.
In fact at high temperatures, the various parameters derived on the basis of
eq. (2) are given by the inverse power of temperature. Also, the approxima-
tion over-emphasizes the energy dependences, the temperature dependence
of t(o) being neglected.

5.1.1. Description in terms ofphaseshijts

Several workers have used the phase shift formalism to describe the tem-
perature dependences of various quantities, an approach which has been
elaborated in considerable detail by Souletie (1975).
The magneticnonmagnetic transition is visualized as a smooth transition
from the magnetic HF solution to the nonmagnetic limit. At high tem-
peratures the phase shifts are different for Q and - 0 while at T = 0,
q,(eF) = q-,(cF). Different parameters thus can be correlated by evaluating
q,(T) and q-,(T) using expressions valid in the H F treatment. The magnetic
susceptibility, for example, is given by

while the impurity resistivity is

Both can be described adequately with the same parameters qa(w) and
q-,(o). The method has been proved to be extremely successful in accounting
for a broad range of experimental parameters for widely different alloys.
The reason for this, however, is not entirely clear, the main objection being
perhaps, that HF treatment neglects spin-flip scattering, which is essential
in the Kondo problem (Stewart and Gruner 1973). Souletie’s approach also
over-emphasizes the temperature dependences. Energy dependences, which
are essential in the narrow resonance level concept, are completely ignored.

5.1-2. Phenomenologicalpicture of resonanceformation

Each of the two alternative approaches discussed earlier proposes a widely
different picture of the resonance formation in dilute alloys. The narrow
resonance level concept relies heavily on the Abrikosov-Suhl resonance
which arises as a consequence of many-body effects; the phase shift approxi-
642 G. GRUNER A N D A. ZAWADOWSKI [CH. 8, Q 5

mation, on the other hand, is based on the Friedel-Anderson single particle

description. Both approaches have been designed to account for the tem-
perature dependences of various macroscopic quantities, and do not aim to
discuss long-range correlation effects. Long-range correlation effects, are,
however, fundamental in the low temperature limit and are closely related
to resonance formation. It is not surprising therefore, that the two models

correlation effects is given by g = v,/2A' with A' -

predict entirely different behaviour. The coherence length for long-range
kT, in the narrow
resonance level model, while Souletie's approach gives ( = vF/2A.For alloys
with kT, < A, this difference is substantial.
Correlation effects were discussed in $4.2.2 where experiments related to
the charge perturbation around the impurities were summarized. The
depression of the charge perturbation in AlMn was shown to be compatible
with an overall energy dependence havinga width r 0.5 eV. The signifi-
N

cance of this result is clear. r is larger than the width of the narrow, many-
body resonance, which in the case of AlMn is about 0.2 eV (see table 1) but
is significantly smaller than the singleparticle width A which is expected to
be larger than 1 eV. The reason for this discrepancy is that various experi-
ments are sensitive to different parts of the scattering amplitude, or of the
density of d-states. Macroscopic experiments sample the energy (and
temperature) dependence within the energy region kT around E ~ as, opposed
to optical experiments which are sensitive to states far from the Fermi level.
The charge perturbation is sensitive to the behaviour of the scattering
amplitude averaged over a broad energy range. The value of r determined
from the behaviour of the charge perturbation then suggests that the density
of states has a sharp top at E~ and broad tails: the former determining the
low temperature macroscopic properties. Correlating this finding with the
theoretical results obtained, it is evident that the sharp top of the density of
states can be associated with the many-body resonance developing at the
Fermi level at temperatures below T K .The broad tails on the other hand
correspond to the single particle resonances, not affected by the low energy
processes associated with the Kondo effect.
The positions of the single particle resonances are determined by U,A
and by N,and the HF approximation of the Anderson model accounts we 11
for these resonances depicted in fig. 2 for AgMn and CuNi. The narrow
central peak which develops at E~ has a m a p x d e determxed by the charge
neutrality, and has a width of the order of kT,. It has a Lorentzian top and
logarithmic tails, as evidenced by the behaviour of the macroscopic properties
and by theories summarized in $4.1.
CH.8, 8 51 PROPERTIES OF KONDO ALLOYS 643

In the strongly magnetic limit U/A9 1 the single particle peaks are at
energy U apart, the central peak is narrow and well resolved. The situation
appropriate for CuFe is shown in fig. 20. Here A and kTK differ by more
than an order ofmagnitude. With a decreasing U ratio the broad Friedel-
Anderson resonances move towards E~ and the central peak broadens
rapidly. For AlMn, U/nA 2 1 and indeed kTK is only an order of magnitude
smaller thand. Finally, for U + 0 the HF picture for a truly nonmagnetic
impurity, i.e. one Lorentzian resonance with a width A, is recovered. The

A4 5 CV
mMy M Y kTfWl CV
(Abrikawv-SuH)
N.6

CF w

Fig. 20. Schematic density of d-states a t T Q T,, appropriate for 9 F e . The width of
the single particle resonances is A and that of the central peak kT,. The shape of the
central peak at high and at low energies is also indicated (GrUner and Zawadowski 1972).

relation between the width of the many-body peak and the single particle
resonances is given by the expression for TK in terms of 9 (eq. 4.4) with 9
given by the Schrieffer-Wolff transformation.
Various macroscopic properties, early optical experiments on strongly
magnetic alloys, together with results on local properties, are in accordance
with this description. Recent optical experiments also support this point of
view. Optical properties of AlMn (Beaglehole and Will 1972) have been
interpreted in terms of this mTdel (Griiner 1974); in CuNi and AuNi alloys
careful experiments (Bassett and Beaglehole 1976; Kaiser and GTkrt 1976)
suggest that serious deviations from the HF nonmagnetic picture occur
644 G. GRUNER AND A. ZAWADOWSKI [CH. 8 , § 5

with the density of states having a sharp top and broad tails indicating that
Up,,(.$ is not much smaller than one in these cases.
With increasing temperature the bound state is progressively destroyed,
the narrow central peak decreases and is smeared out by the thermal fluctua-
tions; above T, only the single particle resonances appear and the impurity
looks like a genuine magnetic moment. Room temperature impurity resis-
tivities in copper and gold, shown in fig. 3, are characteristic of this situation.
It is important to emphasize that the s-d model focuses on the central
peak, the main features of which are well reproduced by calculations. The
broad resonances appear only as a temperature independent potential
scattering background through the Schrieffer-Wolff transformation. The
density of states as depicted in fig. 20 is, moreover, in good overall agreement
with the results of perturbation calculations valid for the symmetric Anderson
model: the central peak and single particle tails are well resolved for strong
Coulomb correlations (see fig. 15). Also, the dominant pole approximation
of the model (Zlatic et al. 1974) leads to a density of states rather similar to
that proposed here on experimental grounds. These approximations cannot
however account for the fine details ofthe many-body resonance, in particular
for the logarithmic temperature dependences above TK.
The central peak aspect of the Kondo problem thus appears to be well
confirmed, and a broad range of experimental information can be interpreted
in terms of this picture. It is also in accordance with theoretical results, in
certain limits of the Anderson model for which the calculations were per-
formed and reliable theoretical solutions are available.

6. Conclusions

Recent experimental and theoretical developments of dilute alloys of 3d

elements with simple metals have been reviewed with particular emphasis on
the low temperature properties.
It is well established by various types of experiments that a model, pro-
posed by Anderson, in which the Coulomb correlations between the d-
electrons and the mixing of d- and s-host states is of importance, is capable
of accounting for most of the experimental findings. Due to the low dimen-
sionality of the problem, correlation effects are of crucial importance. These
have mainly been discussed in the strongly magnetic limit where Coulomb
effects are important. The Anderson model reduces to the so-called s-d
model in this limit, where the well-defined spin of the impurity is weakly
coupled to the host states.
CH. 81 PROPERTIES OF KONDO ALLOYS 645

The gradual transition from a high temperature state -where the impurity
looks magnetic-to a low temperature nonmagnetic state, is a central
feature of dilute alloys. The high temperature properties can be adequately
described by perturbational treatments while at low temperatures Fermi
liquid theory is appropriate. The crossover between the two limits can be
accounted for numerically by using Wilson’s renormalization group method.
It seems reasonable to say that the basic aspects of the dilute alloy problem
are solved but further efforts are needed to arrive at a complete agreement
between theory and experiment. In particular the effect of orbital degeneracy
has not been completely cleared up. This is also the case when the impurity
has less or more than a half-filled d-shell. Only a phenomenological descrip-
tion can be given for these situations; even so this description incorporates
both the single particle and many-body aspects of the problem.
Although the Kondo effect itself is a phenomenon restricted to a limited
class of solids, ideas developed in this field have been proved to be extremely
useful in discussions concerning other phenomena. The relation of the Kondo
problem to X-ray absorption in metals and to superconductivityhas already
been mentioned. Recent developments in chemisorption, surface physics
and in the one-dimensional metal problem are strongly based on approaches
applied first to dilute alloys. The understanding of the many-body aspects
of the dilute alloy problem will certainly influence further developments in
the field of magnetism in metals and also in other fields of solid state physics.

Note added in proof

Berman and So (1978, Phys. Rev. Lett. 40,53) performed careful tunnelling
experiments on junctions doped with magnetic impurities, and obtained
the scattering amplitude as a function of energy in a wide energy range. The
experiments confirm the behaviour of the scattering amplitude discussed in
$4 and 5. The Fermi liquid theory was generalized recently for degenerate
orbitals by Blandin and Nozieres (to be published) and by Mihhly and
Zawadowski (to be published). Yoshimori’s results were recovered only in
the s-d limit for S = 5/2, the general results depend on five nonuniversal
Fermi liquid parameters.

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This Page Intentionally Left Blank
 CHAPTER 9

APPLICATION OF LOW TEMPERATURE

NUCLEAR ORIENTATION TO METALS WITH
MAGNETIC IMPURITIES
BY

J. FLOUQUET
Laboratoire de Physique des Solides, Orsay, France

Progress in Low Temperature Physics, Volume VIIB

Edited by D.F. Brewer
0North-Holland Publishing Company, 1978
Contents

Introduction 651
1. Comments on nuclear orientation 652
1.1. Principles of NO 652
1.2. Application to solid-state physics 657
1.3. Experimental conditions 664
2. Magnetism of an impurity: Kondo effect 669
2.1. Magnetism of an impurity in a nonmagnetic host 669
2.2. The Kondo effect 675
2.3. Influence of the hyperfine coupling 680
2.4. NO in the single impurity study 682
2.5. TKscale. Experimental possibilities of the different hyperfine methods 688
3. The hyperfine field. The origin of magnetism 689
3.1. Atomic structure and hyperfine fields 690
3.2. 3d hyperline fields 691
3.3. 4f hyperfine fields 698
4. Single impurity effects 698
4.1. Weak Kondo coupling 699
4.2. Strong Kondo coupling case 706
4.3. Intermediate coupling 709
4.4. Kondo coupling. Degeneracy of the ground state 710
5. Interaction effects 713
5.1. Magnetism of interaction impurities 713
5.2. Sensitivity of NO to interaction effects 719
5.3. Spin glass behaviour in a NO experiment 720
5.4. Appearance of magnetism due to interaction effects 726
5.5. Kondo lattice or magnetic ordering in cerium compounds 731
6. Other applications 731
6.1. Use of NO in low temperature physics 731
6.2. In nuclear physics 733
7. Conclusion 734
Appendix 737
ReEerences 741
Introduction

The aim of this article is to describe the study of dilute alloys by Nuclear
Orientation (NO). Such investigations have experienced a burst of activity
in recent years, particularly with the elucidation of phenomena related to
the Kondo effect. Parallel to the Kondo problem, considerable attention has
been given to: (i) the description of the impurity magnetism itself, e.g. the
question of the existence of orbital magnetism in 3d materials, the role of
crystalline field effects in rare earths; (ii) the coupling among the impurities
when the impurity concentration increases; (iii) the link between magnetic
impurities and decrease of the superconductivity.
With NO experiments, one can study at almost OK: (i) the appearance
and the behaviour of magnetism for an isolated impurity as a function of
an applied field; (ii) the symmetry of the magnetic interaction when spin
glass behaviour occurs; and (iii) the impurity magnetization even in the case
of a strong magnetic response of a superconductinglattice.
This article is written in a simple form in order to show: (i) firstly for the
solid state physicist the possibilities and the limitation of NO methods in
the study of condensed matter ($ 1); (ii) for the nuclear physicist the funda-
mental interest of the study of dilute alloys ($2). Section 3 describes how
hyperfine measurements such as NO are direct tests of the magnetism
origin. In $4, the discussion is concerned with single impurity effects, mainly
the problem of the Kondo effect, while in $ 5 the different coupling among
magnetic impurities is discussed; $ 6 gives examples of practical applications
in low temperature and nuclear physics.
Finally, my main aspiration has been to convince the reader that the NO
method is a very nice and simple tool to measure the magnetic behaviour of
an impurity and that the relative weakness of some results has mostly been
due to the experimentalists. More precise information can certainly be
extracted especially when NO experiments are combined with other tech-
niques.
It should be pointed out that the given examples are chosen for simplicity
and to provide illustrations of well-defined magnetic behaviour. Most of
the examples are chosen from work performed in Orsay or in Grenoble since
652 J. FLOUQUET [CH. 9, 8 1

I have had the opportunity to look in more detail at the experimental results.
More general references are given in the various tables of results.

1. Comments on nuclear orientation

The measurement of the anisotropy of y rays or particles emitted by radio-

active nuclei of spin 1 touches on several different domains in physics:
nuclear physics (determination of nuclear dipole and quadrupole moments,
experiments on parity conservation, mixing between different transition
multipolarities), atomic physics (existence of hyperfine coupling), solid state
physics.
It will be explained in the following why a well-defined quantum state of
spin I with a 2 angular momentum 1, = M emits radiation with an angular
distribution which is characteristic of this state and what are the mechanisms
responsible for the selection of a pure quantum state.
In order to give some practical support to this section, I shall describe
briefly how an actual experiment is performed. The reader who wishes a
more precise description should refer to the general review of Blin-Stoyle
and Grace (1957), De Groot et al. (1965) or Shirley (1966) on NO and the
book of Freeman and Frankel on hyperfine interactions (1967).

1.1. PRINCIPLES
OF NO

I .I .I. SimpIe considerations on nuclear orientation

Nuclear orientation is the ordering of nuclear spins in space. For example

such ordering may occur for a nuclear spin 1 subjected along the Z axis of
quantization to an applied field H if the population of the state 1 I, 1, = M)
is higher than that of the other 21 sublevels. Such ordering can be observed
by various techniques like magnetization, NMR, polarized neutron scattering
or by detection of the angular distribution of particules or y rays emitted by
the nuclei. The nuclear ordering can be obtained dynamically or statically.
The method called nuclear orientation which will be described here, is
restricted to static nuclear ordering detected by the angular distribution of
particles or y rays emitted by radioactive nuclei during their decay. The
population of the 21+1 nuclear sublevels is governed by the Boltzmann
factor aM = exp(-E,/k,T) which contains the ratio of the energy E M of
CH. 9, 8 11 METALS WITH MAGNETIC IMPURITIES 653

the state 11, M ) and the thermal energy k,T. To obtain an appreciable
nuclear ordering, the thermal energy must be comparable to or smaller than
the splitting energy E,-E,-, between two nuclear sublevels. In order to
give an order of magnitude, we note that for nuclei with dipole moments of
one nuclear magneton in an applied field of 100 kOe, the Zeeman energy
is equal to the thermal energy at 3 mK. In solids, as we will see later, such
ordering may occur easily via the hyperfine coupling which produces an
effective field Herron the nuclei of up to 1 MOe.
The main point of the NO methods is that the angular distribution of
the emitted a, 8, y rays is characteristic of the initial state. To illustrate this
point, we take the simple case of a spin Z = 1 which decays to a ground
state Z = 0 by a dipolar y transition (fig. 1). The angular distributions W r
of the y rays emitted from different sublevels II, M) in a direction Z' which
make an angle 0 with the Z axis of quantization are:

W: = w;~
= +a2[l+cos2e], w: = u2 sin28.

At high temperatures, when all the sublevels are equally populated, the
observed angular distribution, which is the sum of each component, is
isotropic. In the opposite situation, when only one state is populated, the
angular distribution is strongly anisotropic. For example a detector along
the Z axis records no counts if only the I1,O) state is populated. The solid
state physicist will explain why the 11,O) state is the lower level and what is
the origin of the splitting between the different sublevels. As the transition
from the different sublevels 11,M) cannot be observed directly due to the
poor resolution of the detector, the observation of a pure IZ, M) state is
obtained by lowering the temperature.
It is worth pointing out at this stage the relation of NO to other nuclear
techniques. In an angular correlation experiment the selection of a pure
IZ, M) state is realized by the condition that a photon emitted from the
intermediate IZ, M) nuclei must be in coincidence with the photon which
has selected this intermediate state. In a Mossbauer experiment, the (Z,M)
selection of the source nuclei (or absorber) is achieved by the Doppler shift
of the absorber (or source).
Finally we must remark that the equality W i = W;' in y ray measure-
ments is due to parity conservation in a y transition. As a state 11, 1) cannot
be resolved here from a state 11, - l), the sign of the effective hyperfine
field cannot be determined but only its magnitude. More generally a y
654 J. FLOUQUET [CH.9, $ 1

anisotropy measurement does not detect the first moment of the orientation
of the nuclei B, which is proportional to the average value of M y

If 80

n E’

FP ( 0 )

bu a dr up0 lor intcr ac t ion

:1
72’ ( 8 )
0
Mognctic intkoetlm
+I -
-Q
-1 -
Fig. 1. Electric dipole radiation. The main point is that the photon has only angular
+
momentum 1 or - 1 along its direction of motion.

but rather the alignment which is an even function of the M quantum

number. The first even moment B, is proportional to the thermal average
defined by :

B2 N (M2-+Z(Z+ 1)).
CH.9, 0 11 METALS WITH MAGNETIC IMPURITIES 65 5

On the other hand, /3 transitions which violate parity conservation are

sensitive to the B, parameter. If the circular polarization is detected, the
sign of the effective hypefine field can be deduced.
As most NO experiments are performed by y anisotropy measurements
we restrict now the following discussion to the observation of y transitions.

1.1.2. Mechanism of Orientation

In insulators, the different mechanism of nuclear orientation are well
described by the following Hamiltonian (Abragam and Pryce 1951)

where Hx, Hy, H, represent the components of the applied field, Z and S
are the nuclear and electronic spin of the observed atoms, A and B are the
magnetic hyperfine coupling between Zand S, D is a possible anisotropy of S
due to crystal field effects and P is the quadrupolar anisotropy of I due to
the coupling between the nuclear quadrupole moment and the electric field
gradient.
The use of the first term leads to brute force polarization of the nuclei.
To achieve appreciable orientation, large magnetic fields and very low
temperatures must be employed, Such experiments can be useful principally
for nuclear physics.
By the combined effects of the Zeeman electronic term and the hyperfine
magnetic coupling (A, B), nuclear orientation can be achieved with relative
low applied fields since the electronic moment is polarized with a small
applied field and the corresponding hypefine field ASz/gnpncan reach
1 MOe. This mechanism, proposed by Oorter (1948) and Rose (1949),
describes the case of a free paramagnetic impurity.
When a strong anisotropy exists (DS;),its conjunction with the hyperfine
magnetic cciupling gives appreciable NO even in zero field (Bleaney 1951).
This mechanism has been used extensively in the study of paramagnetic
salts, the radioactive ions being either a constituent of the salt or a sub-
stituted ion.
Pound (1949) suggested that the quadrupole term P leads to nuclear
alignment even in zero applied field. Generally, the quadrupolar nuclear
splitting is lower than the two previous Gorter, Rose and Bleaney cases.
656 J. FLOUQUET [CH.9, !j 1

The Abragam and Price Hamiltonian neglects completely the effect of

conduction electrons. Directly applied to metals, it leads for example to the
conclusion that no hypertine coupling occurs for a diamagnetic impurity
aside from the brute force term.
In 1959, Samoilov et al. showed by NO that a strong orientation can be
reached for diamagnetic impurities dissolved in ferromagnetic lattices. The
essential role of conduction electrons was explained later by Daniel and
Friedel (1963). With the case ofthe Kondo effect, we shall see later another
example of the major influence of the conduction electrons.

1.1.3. Generalformulation
Generally, y decay is more complicatedthan in our first example: the observed
y ray follows several or y transitions (see practical examples on fig. 2). The
expression for the y distribution is simple if the following conditions are
respected:
(i) The parent nuclei 1 I, M ) are in thermal equilibrium with the lattice.
(ii) The Hamiltonian of the parent nuclei or intermediate nuclei has a
cylindrical axis 2 of quantization.
(iii) The lifetime of the intermediate nuclei li is shorter than the nuclear
relaxation time in order to ensure that no re-orientation occurs in the inter-
mediate levels.
All these conditions are easily obtained when the lifetime of the parent
nuclei is long enough to be sure that the nuclei are in thermal equilibrium
since the lifetime of the intermediate state is generally very short (fig. 2).
Assuming these restrictions, the angular distribution of the y ray, emitted
at angle 0 with respect to the 2 axis, is given by the general expression

w(e)= K gKBK U,F,pK (cos 0)

where gK is a solid angle correction which characterizes the detector, U, is a

nuclear parameter which describes unobserved nuclear transitions, F K is a
nuclear parameter which describes the observed transition, pK(cos8) iS a
Legendre polynomial and BK is a nuclear orientation parameter which is
related to the population W(M)of the parent nuclear sublevel. The series is
restricted to even values of K in order to respect the y parity conservation.
We will assume here that in all the decays observed, the nuclear parameters
g&#K are well known, The solid state information is given by the two
terms B,P,(cos 0).
CH. 9, 8 11 METALS WITH MAGNETIC IMPURITIES 657

52u"

-37
p'33% 3,
E C 56%

€2 835
2'
54~r

"cr

5%
7.1 d

5*

0.7pr
1,332
0'
Fc5a 6o Ni
Fig. 2. Radioactive decay of "Mn, 5AMn,"Co, 6oCo.The broad arrows correspond
to the NO observedyrays. The angulardistributionsof these y raysare drawn on figs.3 and 6.

1.2. APPLICATION
TO SOLID-STATEPHYSICS

1.2.I . Hyperfne coupling-nuclear orientation parameter

The BR terms depend on: (i) nuclear constants such as nuclear dipole or
quadrupole moment; (ii) solid state parameters which describe the NO
mechanism; (iii) the temperature. Knowledge of two of these items will
determine the third. The method can be used for nuclear, solid state physics
or thermometry at low temperatures. We restrict the discussion here to the
solid state applications.
The general BK expression is given by

B&) = 1
M
(2K+ 1)' + C[IKI, MO] W ( M ) , (1.1)
658 J. FLOUQUET [CH. 9, Q 1

where C[IKZ, MO] is the well-known Clebsch-Gordan coefficient. The

information given by NO experiments results from the comparison of the
experimental value W(0) with the theoretical value computed for different
hyperfine couplings. Table 1 indicates the B,, B, terms for three simple
Hamiltonians in the high temperature limit for the special case of a nuclear
spin I = 1 and electronic spin S = 3 (Blin-Stoyle and Grace 1957, p. 564).

Table 1

The first nuclear orientation parameters for three simple nuclear orientation mechanisms
(r= 1, s = +).

Harniltonian B1 Bz

Wc see from this table that y-NO experiments cannot detect the sign of
He,, but only that of P - that the separation between a quadrupole and a
magnetic coupling can in principle be obtained at high temperature where
the respective B, terms show quite a different temperature dependence.
All the above discussions assume that all the observed nuclei have the
same axis of quantization which means practically that a macroscopic axis
of symmetry can be defined which coincides with the local axis. As we will
show in $ 5 , we must check whether or not this condition is fulfilled in a
given case.
We have drawn on figs. 3-6 the y anisotropy of well-known 3d NO isotopes
"Mn, s4Mn, 58C0,6oCowhich correspond to the y decay of fig. 2. All the
nuclei are subject to an effective hyperfine field equal to +200 kOe. We
must remark: (i) that the low temperature sensitivity depends on the relative
sign of the U,F,, U4F4 terms. This effect is shown by comparing the 58C0,
fig. 5, with the 6oCo, 'Mn, figs. 3,4 and 6 and noting that the "Co U4F4
term has an opposite sign to the U,F, term. While the 52Mn,54Mnand 6oCo
have their maximum sensitivity in the axial direction, the 58C0loses its
sensitivity completely along this direction. (ii) that the sensitivity of the
CH. 9. 0 11 METALS WITH MAGNETIC IMPURITIES 659

nuclear probe to any misalignment between the real 2 axis and the experi-
mental Z axis (defined generally by the applied field) depends on the strength
of the ratio U4F4/U,Fz when both terms have the same sign (see fig. 3 for
"Mn and fig. 4 for 54Mn).(iii) that with a relatively low counting rate the
accuracy in the determination of an effective field can approach one percent.

1.2.2. Illustrating cases

Before 1964, most of the nuclear orientation experiments were performed

with paramagnetic salts which were cooled down by demagnetization of the
salt itself. Now, most of the NO experiments are performed in metallic
materials which are cooled indirectly using an auxiliary demagnetization salt
or dilution refrigerator; the main experimental difference is that the pro-
duction of the low temperature is independent of the sample preparation. In
the actual studies three different fields can be distinguished:
(i) measurement of hyperfine fields in ferromagnetic materials,
(ii) measurement of hyperfine interactions in the presence of radiation
damage,
(iii) study of dilute magnetic alloys.
The first two subjects are often studied using nuclear resonance destruction
of the y ray anisotropy (NMR/NO). We do not describe here the details of
this method (destruction of y anisotropy by a radiofrequency field at the
saturation conditions for the nuclear resonance) since generally the NMR
detection is not easy in the case of a magnetic impurity dissolved in non-
magnetic metals due to the fast nuclear relaxation times of the impurity
(Waltstedt and Narath 1972). In this case, the NMR/NO detection adds the
supplementary disadvantage of a radiofrequency power limitation to the
maintenance of low temperatures (Spanjaard et al. 1971). The recent review
by Stone (1976) gives interesting applications of NMR/NO.
In order to illustrate the NO impact in solid state physics, we have shown
in table 2 different experiments which have been performed. Four examples
are related to metal physics, two examples to insulators. The first y anisotropy
signal was observed in 1951 at Oxford and at Leiden by the detection of the
6oCo anisotropy emitted from Co nuclei, dissolved in a single crystal of
CuSO4RbZSO46H,O(tutton salt) (Daniels et al. 1951; Gorter et al. 1951).
The more famous NO experiment is the observation of the B decay non-
parity conservation (Wu et al. 1957).
660 J. FLOUQUET [CH. 9, g 1
m
.-
d
LL
 58 60
co co

Fig. 5. Fig. 6.
Figs. 3-6. The figures represent the y ray distribution W of the respective "Mn, 54Mn, "Co, 60Coprobes, submitted to a hyperfine field of
200 kOe, for five different temperatures T.The nuclear parameters defined in eq. (1.1) are:
zMn 54Mn WO 60Co

Z 6 3 2 5
g&nl@rJ 3.07 3.30 3.99 3.75
uzF2 -0.3741 -0.4949 -0.2988 -0.4206
uz4 -0.1591 -0.4467 +0.7127 -0.2428
662 J. FLOUQUET [CH. 9, 1

Table 2
Examples of NO experiments.

Experiments' Comments References

-
CO6OCO First observation of a hyperhe field in a
ferromagnetic metal
Grace et al. (1955)
Khutsishvili (1955)
98Au First observation of a hyperfine field on a SamoYlov et al. (1959)
diamagnetic impurity in a ferromagnetic
metal
&iS4Mn First experiment performed in dilute alloy Cameron et al. (1964)
E60Co Detection of the NMR by NO Matthias et al. (1966)
137mCein CMN Determination of the absolute temperature Huntziger et al. (1970)
scale of CMN
"Mn in (CL)MN Rotational cooling Lubbers et al. (1967)

'CMN, (CL)MN are abbreviations for cerium magnesium nitrate and cerium lanthanum
magnesium nitrate, respectively.

1.2.3. Limitation of the method. Comparison with other methods

In order to emphasize the interest of such measurements, we describe the

advantages of the technique. The main advantage is that NO observations
are single counting experiments which allow a low content of radioactive
nuclei, typically 10' atoms; the corresponding concentrations are generally
less than I ppm. Other advantages are:
(i) large range of isotopes available, notably of 3d elements (V, CryMn, Co)
and 4f elements (Ce, Eu, Tb, Yb);
(ii) high energy of the observed y rays (see fig. 2), typically 500 keV, which
allows working with bulk materials easily characterized by other techniques
(resistivity-magnetization) ;
(iii) its detection entails no resonant condition. The main disadvantage of
the method is its integral character which does not allow the direct decom-
position into different hyperfine couplings (see 0 5). The interpretation of the
results will be unambiguous if the physical situation is simple, for example a
simple magnetic or quadrupolar coupling. The interpretation becomes more
difficult in the presence of a mixed hyperfine coupling or of different sites in
the lattice. Experimentally, the assumption of an unique hyperfine coupling
must be checked over a large range of temperature. Unfortunately, this
condition is often not realized in many experiments which have been reported
up to now.
CH.9, 8 11 METALS WITH MAGNETIC IMPURITIES 663

NO gives the same information as ordinary magnetization experiments (M)

with somewhat more sophisticated response and no background signal due
to the lattice. The main difference is, as described in figs. 3-6, its higher
sensitivity to any local breakdown of the macroscopic symmetry defined by
the external field (see 0 5). The other differencesare: (i) its specificity (observa-
tion of a well defined nucleus); (ii) its hyperfine character which is more
sensitive to the different magnetic terms since for example spin and orbital
contributions give quite different hyperfine response (see 0 3).
Hyperfine measurements such as differential perturbed angular correla-
tion, Mossbauer effect or NMR which are spectroscopic methods are more
powerful techniques. Unfortunately conditions on the hyperhe coupling
and on the electronic or nuclear relaxation time limit their practical range of
investigations. NO is often more easy to perform and can be a good tool to
continue studies which cannot be carried on by NMR; an example will be
given in 5 5 for the AuCo alloys.
Another possibilityfor detecting a static thermal NO effect is offered by
determining the intensity of the Mossbauer lines which depend on the parent
or stable nuclear populations if the source or absorber is at a low temperature.
If a source like PtS7Cois cooled to sufficiently low temperature so that the
' 7C0 parent nuclear sublevels become unequally populated, the intensity of
the Mossbauer lines depends both on the population of the '7C0 parent
nuclei which is a function of the "Co effective field, and on the transition
probability between the different 57Fe Mossbauer sublevels. Such NO is
observed at higher temperatures than in an ordinary experiment since the
variation of the corresponding intensity depends on the first order para-
meter B,. In comparison with ordinary NO the disadvantage is generally
the higher impurity concentration related to the low energy of the Mossbauer
y rays; the advantages are: (i) only intensity ratios in a single spectrum are
necessary. This leads to less possibility of systematic error than NO where
warm counts must be obtained; (ii) no external magnetic field is necessary
to provide a quantization axis.* For an absorber such measurements are of
rather low utility despite the fact that the same phenomenon is able to give
directly the temperature and the hyperfine coupling of the sample nuclei
through their Mossbauer line splitting and intensity strength (Kalvius et al.
1970).
The nuclear specific heat anomaly C, is directly linked to the hyperfine
coupling. The advantage here is that the magnetic coupling can be determined
*Gonzales Jimenez et al. (1974) have observed the orientation of a paramagnetic state at
low temperatures in zero field for the first time for a cubic symmetry impurity.
664 J. FLOUQUET [CH. 9, 0 1

in zero field and eventually in an applied field. The disadvantage is that the
impurity concentration must be high enough to overtake signals arising from
other contributions. Its comparison with NO or M is powerful for investiga-
ting the presence of different sites since C, has a rather specific response for
magnetic or non-magnetic sites. Its efficiency will be shown in 0 5.

1.3. EXPERIMENTAL
CONDITIONS

In a nuclear orientation experiment, three different parts can be distinguished

(i) the attainment of low temperatures,
(ii) the detection of y rays,
(iii) the preparation of samples.

1.3.1. Refrigeration and y ray detection

The necessary low temperatures can be achieved by adiabatic demagnetiza-

tion of a paramagnetic salt or by dilution of 3He in 4He. By demagnetization
of cerium magnesium nitrate (CMN), temperatures down to 3 mK can easily
be reached on a sample thermalized at the end of a thermal link in contact
with the salt (Williams 1968); with commercial dilution refrigerators, most
of the experiments reach temperatures near 10mK. In the future more
fruitful solutions for NO seem to be:
(i) demagnetization of enhanced nuclear moment compounds (PrNi, ,
PrCu,) where temperatures down to 1 or 2 mK, respectively, can be reached
(Andres 1976);
(ii) attainment of a continuous temperature down to 3 mK by dilution
refrigerators using either high surface heat exchangers (Frossati et al. 1976a*)
or multimixingchamber systems (De Waele et al. 1976). Whatever the method
of attaining the low temperature, the experiment must be performed in a
wide range of temperature. At the present time, the best results seem to be
obtained with the old technique (demagnetization) where the temperature is
continuously varied during subsequent heating of the salt.
The counting system is an ordinary single counting arrangement. Two
types of detector can be used: (i) ordinary NaI(T1) scintillators which have
a poor resolution but a high efficiency; (ii) Ge(Li) detectors which have a
high resolution (-2 keV) but a lower efficiency. If all the nuclear parameters

*Frossati has recently reached a continuous temperature of 2.7 mK.

 CH. 9, 8 11 METALS WITH MAGNETIC IMPURITIES 665

are well known in the y expression of the y ray distribution only one detector
need be used. The experimental parameter, measured usually in the direction
of the applied field, the so-called axial anisotropy E(O), is defined as the
differencebetween the warm and cold counts normalized by the warm counts

E(0) = ""(0) -"(O)]/N"(O).

The NO results are reported often in terms of an effective hyperfine field,
Herr, which corresponds to the experimental value E(0) calculated from a
brute force-type Hamiltonian:

A more satisfactory solution is to use two counters parallel and perpendicular

to the macroscopic axis in order to have two self-consistent measurements
E(0) and E(3n) at the same time.
Each experimental point is obtained by the comparison of two y ray
measurements: (i) the y anisotropy E,.(O) of an isotope A with a known
hyperfine coupling; (ii) the y anisotropy of an isotope B with an unknown
hyperfine coupling. E(T) will define the B temperature. Figure 7 shows the
general set-up used at Orsay. A CMN salt is demagnetized and temperatures
down 3 mK are obtained on the sample which can be polarized in fields up
to 40 kOe. The electronic pulses received from the detectors are amplified
and analyzed in amplitude in a multichannel analyzer following a 10-minute
cycle. Each point is stored on a paper tape which is then analyzed by a
computer for an automatic research of the y ray photopics. This procedure
minimizes the eventual electronic drifts. Simultaneously, direct integral
measurements allow a crude analysis of the running experiment. Using
simple electronic devices, a NO apparatus can be almost automatic and must
be regarded as the equivalent of a NMR or Mossbauer spectrometer (Benoit
1976). A more important point is the sample preparation, which we now
make some comments on.

I .3.2. Metallurgy
The activity of a NO sample is typically around 10 pCi which corresponds
to 10" nuclei with a lifetime T of one month. The local impurity concentra-
tion will depend on the modes of preparation which can be classified as
follows :
666 J. FLOUQUET [CH.9, 5 1

(i) ordinary metallurgy,

(ii) direct activation,
(iii) implantation.
The last of these can be su,divided into direct implantation after a nuclear
reaction, or indirect implantation using an isotope separator.
Timer

Fig. 7. NO set up of Orsay (Benoit 1976). The main point is that the exchange gas,
which ensures thermalization of the paramagnetic salt with the 1.5 K fixed point, is scaled
at 4.2 K.This NO spectrometer can carry out automatically two full runs including cold
and warm counts. h is the 1.5 K fixed point, i and j are respectively the demagnetization and
polarizing magnet, k is the paramagnetic salt, I a 50 Hz heating, m the Ge(Li) detector,
A the NO thermometer (for example e 6 0 C o ) ,B the NO sample (for example G s 4 M n ) ,
MA the multichannel analyzer, CS the current power supply, S the shunt which measures
the current in the polarizing magnet, V two voltmeters. The spectrum represents a typical
NO measurement in a G S 4 M n , e 6 0 C o experiments. The clocks 1, 2, 3, 4 d e h e res-
pectively the time of (1) the demagnetization salt, (2) the cold counts, (3) the 50 Hz reheating
of the salt, (4) the warm count normalization. A resistor bridge R gives continuously the
temperature of the paramagnetic salt. For each 10 min top given by the analyzer, a serializcr
picks up successively the information received from the different measurements.
CH. 9, 8 11 METALS WITH MAGNETIC IMPURITIES 667

A radioactive sample can be prepared in a classical way by diffusing the

radioactive isotope in the metallic sample or melting together both materials.
As a practical example, we describe a C U ~ Alloy ~ Mpreparation.
~
54Mn can be bought in a carrier-free chloride solution: 'carrier-free'
means that there are no substances other than HCl, H,O, Mn. In order to
eliminate parasitic ions like iron, the best method is to clean this solution
using an ether or a resin separation. A small part of this purified activity is
electropolated or directly painted on the Cu sample. In the first case, the
active sample is generally melted using a high-frequency induction furnace;
in the second case, the chloride is decomposed and diffused during annealing
under a hydrogen atmosphere; further homogenization can be obtained by
melting the sample. (If the chloride is decomposed during the melting the
first step can be bypassed directly). Finally, the activity is thus diluted
homogeneously in the sample which can be characterized by other techniques;
the important point is the low concentration of radioactive nuclei (< 1 ppm).
Direct activation can be induced in stable alloys by different types of
particles (neutron, proton, deuteron). Generally as the concentration of the
stable impurity must be rather high (> lo00 ppm), two problems may occur:
(i) magnetic interactions among the impurities; (ii) disturbance of the lattice
symmetry. One example is given by the preparation of the La137mCealloys
which can be directly obtained by bombarding a La foil byaproton beam.
We obtain a high dilution of the magnetic impurities, but also the disadvan-
tage of a lattice disturbance produced by the incoming particles and by
the recoil of the created radioactive ions.
Around 1967, implantation techniques seemed sufficiently powerful to
prepare any type of alloy using an isotope separator plus a post acceleration.
To illustrate the principle of the method, we describe the preparation of an
-
AuYb alloy. Two radioactive isotopes seem available for a NO study:
"'Yb and 169Yb.As a first step, the Yb203oxide is irradiated in a neutron
reactor in order to get the desired activity. This powder is then set in an
isotope separator where two different beams of and la9Yb can be
extracted separately. Using a post acceleration of 100 keV, these incoming
ions are selectively implanted in a gold lattice with a penetration depth
ranging to about 100 A. This leads to a local concentration around 100 ppm.
If we compare the implantation to a direct activation its advantages are the
selection of a well-specified isotope and a greater dilution. However in all
this picture we have completely neglected the defects produced during
implantation: each incoming ion produces around lo00 defects before it
stops completely. The problem is to know what alloys we are studying. A
668 J. FLOUQUET [CH. 9, 5 1

'
simple comparison of an Au' 5Yb implanted sample with the same sample
melted after implantation(Ben0it et al. 1974) clearly shows that they are not
equivalent (fig. 8). In implanted samples, the Yb ions are far from the idea-
lized situation of substituted ions in an unperturbed lattice. As our task is
not to describe the physicsof radiationdamage, weconclude that the separator
implantation is a very nice tool to select the activity and only a first step in
the preparation of a dilute alloy. Classical metallurgy must then be performed
in order to eliminate the radiation damage and to obtain finally a simple
alloy.

- 20
(TI
Yb

-1s

Eb
-l a

of 283 KeV
-!
rbrultr for

I
/:+'-
,'
H 3 10 kOe
.2'5Eamelted after implantation
.'~Ebimplanted, aarnple

25 50 l5 +K-'

Fig. 8. Anisotropy of the 283 keV y ray of the '"Yb probe implanted in a gold lattice
(P) or melted after implantation (E.).(Benoit et al. 1974a.)

When a heavy nuclei of mass M is submitted to a nuclear reaction by a

light particle of mass m and of energy Eo ,the produced radioactive nucleus
has a recoil energy around:
 CH.9, 5 21 METALS WITH MAaNETIC IMPURITIES 669

As charged light particles (a, p, d) must have a rather high energy in order
to lead to appreciable nuclear cross section a high recoil energy (typically
500 keV) is obtained. This energy can be used to perform a direct implanta-
tion in another lattice. A typical arrangement consists of first a thin foil,
where the nuclear reaction occurs, followed by a second foil, where the ions
recoil.
Such a procedure was realized previously in Berkeley (Brewer 1969) in
order to prepare a Cu5*Mn sample. The "Mn activity is produced by a
(a, 3n) reaction on avanadium foil with 33 MeV incoming a particles. The
average penetration depth is typically around lOOOA. Eska et al. (1976)
have recently used the same procedure for a AuMn alloy using the supple-
mentary property that the influence of the other magnetic impurities can
be minimized by a previous oxidation, which does not oxidize the incoming
ions which are further implanted at room temperature. As we have under-
lined before, the main problem remains the annealing of defects. Careful
investigations must be made in order to be confident of its valid application
to the study of dilute alloys. In conclusion, I would like to emphasize that
(i) ordinary metallurgy can be performed with radioactive samples; the
main difficulty, coming from contamination troubles, is easily solved as the
usual activity is very low. (ii) special techniques like implantation can be
employed successfully for qualitative investigations (is an impurity magnetic
or not in such materials?) but certainly not for more accurate quantitative
studies.

2. Magnetism of an impurity: Kondo effect

2.1. MAGNETISM
OF AN IMPURITY IN A NON-MAGNETIC HOST

2.I . I . The Friedel approach (Blandin 1973)

The problem of a magnetic impurity in a metal was first treated with the
exchange Hamiltonian (Zener 1951)

which describes the coupling of the spin S of a local moment interacting

with the conduction electrons of spin s. Since the existence of a localized
spin is assumed in this Hamiltonian from the beginning, it is not appropriate
to ask why 3d impurities have or have not a local moment.
670 J. FLOUQUET [CH. 9, 4 2

An important advance in such understanding was initiated by Friedel

(1956) who used a resonant scattering theory within an unrestricted H F
approximation. The presence of an impurity produces a local spherical
potential V(r) which scatters the free electrons of the metal (Friedel 1952).
The important point is that the extra-ionic charge 2 associated with a foreigh
atom is screened out over a distance of an atomic radius (charge neutrality)
apart for long-range oscillations of the electronic density p(r),
p(r) = -(u/2nr’) cos (2k,r +$),
k,, r being respectively the Fermi wave number and the distance from the
impurity, and u, 4 are parameters depending on the scattering by the
impurity.*
When the potential V ( r ) is nearly strong enough to create a bound state
with quantum number I, resonance scattering occurs. Such a situation is
well known in atomic and nuclear physics. The virtual bound state, which
resonates with the I spherical component of the plane waves, is characterized
by a finite broadened width (A) and a position ( E ) near the Fermi level. As,
in this virtual bound state, the electrons are well localized, local exchange
and correlation forces ( V ) must be taken into account; they favour spin
alignment according to the Hund’s rule. Using these arguments, Blandin
and Friedel (1959) predicted the occurrence of 3d impurity magnetism as a
function of the electronic parameters of the lattice (influence on the A width)
and of the impurity (influence of the screened charge and the correlation
forces). Similarly, they showed (Blandin 1961) that when the spin degeneracy
is lifted in a virtual bound state, the oscillating charge density in the matrix
is associated with an oscillating spin density of the same wavelength;? this
leads to a Rudermann-Kittel-like oscillation (1954) and to a spin glass
coupling among the impurities which can be characterized by an isotropic
distribution of the blocked local moments (Blandin and Friedel 1959).

2.1.2. Anderson Hamiltonian

In 1961, Anderson derived a simple Hamiltonian which is equivalent to the
Friedel approach (Daniel and Friedel 1966). The Anderson Hamiltonian is

*This phenomenon is basically the diffraction effect known in optics. The impurity can
be regarded as a hole which disturbs the homogeneous crystal.
tThe scattering by a spin dependent potential in normal metals was discussed first by
Friedel (1952) for the problem of a proton with its bound electron dissolved in a simple
Fcrmi gas.
CH.9, Q 21 METALS WITH MAGNETIC IMPURITIW 671

widely used for theoretical investigations using the HF approximation. It is

given by

The first term is the band Hamiltonian, CG being the creation operator in
the conduction band. The second and third terms describe the local d
state of the impurity (the creation operator Cde of a d electron of spin
a). The d state with one electron has energy Ed, the d state with two
electrons 2Ed+U.The interesting case will be when Ed c EF and Ed+U >
Ep (fig. 9). The last term Vkd describes the resonant scattering and leads
to the virtual bound state picture (fig. 9). The mixing vk, gives rise to a
broadening A of the localized state,

PO
I P-0

Fig. 9. The d bound states of energy Ed and 2Ed+ U are shifted and broadened by the
resonant scattering with the conduction electrons.
672 J. PLOUQUET [CH.9, 4 2

( p being the density of states of the conduction electron at the Fermi level)
and to a shift of d-a virtual levels with respect to the Fermi level (energy
shift).
In the HF approximation, the Coulomb interaction inside the d level is
approximated by the relation

where (nd-,) describes the average occupancy of the d-a level; fluctuations
between electrons of opposite spin a -u are completely neglected. With this
restricted approximation, for the above model of one d electron, the occur-
rence of magnetism necessitates the following condition

A non-magnetic impurity is described by the picture of two virtual d levels

at the Fermi level. In real cases (orbital degeneracy), the general magnetism
condition is given by a Stoner-like condition between the pd density of states
of the virtual bound state at the Fermi level and Uerr, an effective
interaction :

Figure 10 represents the 3d magnetism occurrence along the 3d elements

as a function of the strength of the ratio A / U ; the sharp line shows the tran-
sition in HF theory between a non-magnetic regime where (n,,) = (nd-,)
and a magnetic regime where (n,,) # (n,,). While it has long been
evident that the sharp demarcation between magnetic and non-magnetic
impurities is an artifact related to the Hartree-Fock approximation, because
there must be no sharp phase transition for one impurity, it is only recently
that a unified view has been put forward in the theory of the Kondo state.
In the limit where the positions of the virtual bound states with opposite
spins are well above and below the Fermi level as pictured in fig. 9. Schrieffer
and Wolf have shown that the Anderson Hamiltonian can be reduced to an
exchange part and a classical potential V,,

HR= +JS*s+V,.

The essential point is that the resonant mixing Vkd leads to a positive anti-
ferromagnetic J constant which can be defined as a function of the d virtual
bound state by the relation
CH. 9, 8 21 METALS WITH MAGNETIC IMPURITIES 673

The positive sign of J is thus a characteristic of a resonant mixing as the

usual direct atomic exchange would give a negative J value.
Practically, the exchange Hamiltonian describes only the situation of the
Mn impurity in a normal lattice. Although the Anderson Hamiltonian is
more suitable than the exchange Hamiltonian for describing the variety of
dilute alloys, the latter is more simple and important results have been
obtained from it. In the following sections, the normal potential is neglected;

Ti Mn NI T
H.F picture
Fig. 10. Schematic representation of the condition for formation of a local moment in
the Friedel-Anderson model (Hartree-Fock approximation). Impurities outside the curve
are non-magnetic (NM); the diagram is for 3d impurities in a simple metal host.

only the exchange part is taken into account since we discuss the magnetic
properties of strongly magnetic HI; impurities. It must be emphasized that
the spin value S attributed to an impurity is not only specific to the initial
unperturbed d state but partly given by the HF treatment of the conduction
electron mixing ( Vkd).
A quantitative description of the magnetic phenomena can be given
when the conduction band is more complicated than a free electron structure.
Phase shift analyses have been performed by Friedel et al. (1966) for narrow
bands and applied to Pd, Pt lattices by Campbell (1967). This problem has
been extensively studied by Moriya (1967).

2.1.3. Response of an electron gas to the impurity magnetism

In order to avoid a complex discussion, we present here the crude picture
given by Anderson (1967) and consider the simple form of the exchange
614 J. FLOUQUET CH. 9.0 2

Hamiltonian. Reducing the S vector to an ordinary number S, its action on

the electron gas can be summarized by linear response theory. The polarized
center S at the site ro perturbs the free electron gas by the local presence of
an effective field H(ro) SJ. The electronic response at site r , rn(r), depends
N

on the spatial susceptibility of the lattice x(r-ro),

If the interaction among the conduction electrons can be omitted (case of a

normal metal like Au), the spatial susceptibility has the well-known shape of
the RKKY oscillations given by the function Fo(r)equal to [Ruderman and
Kittel 1954; Yosida 19571 :

Fo(r) - -i3-
r:x-cos x], x = 2k,r.

This magnetic polarization carries the magnetic information and will be

responsible for magnetic interactions among the impurities. The energy of
interaction between impurities localized on sites r l , rj is given by

As (i) F(r) oscillates far from the impurity site and (ii) S has 2S+ 1 degrees
of freedom, in low concentration ranges the magnetic ordering among
impurities corresponds to magnetic moments isotropically coupled without
any preferred direction. (Caroli 1967 has computed the resonant interaction
process using directly the Anderson Hamiltonian.)
In some lattices like Pd, Pt which have an enhanced Pauli susceptibility,
the interaction among the conduction electrons cannot be neglected. The

well-definedsign over a range d which covers many atomic distances (d 8 A-

main result is that the spatial susceptibility has an enhanced response with a

for the Pd lattice). This enhanced response leads (i) to an abnormal polariza-
tion of the lattice around the impurities. This gives rise to the giant moment
phenomenon (fig. 11); the magnetism of the impurity is not only localized
on its sites but is accompanied by the electronic response magnetism which
is carried by the surrounding atoms up to a distance equal to d (the giant
moment of iron in palladium is near 1 2 ~ ~(ii) ) ; to a fcrromagnetic coupling
among the impurities inside the ferromagnetic polarization clouds.
CH. 9, 0 21 METALS WITH MAGNETIC IMPURITIES 675

2.2. THEKONDOEFFECT

2.2.1. Simple considerations

In 1933, experimentalists had already observed that the resistivity Of

metal samples thought to be very pure has a minimum at low temperatures.
As the resistivity of pure metals decreases as the temperature decreases, it

I \‘*\El
\C
\

I \ \ /

lst ncighbour

Fig. 11. The full line A describes the spin polarization of a normal host as a function of
the distance r from the impurity site. The dashed curves B and C correspond to the
schematic spin polarization of an enhanced lattice; the curve B describes the case of an
induced moment, located on the matrix sites, weaker than the moment which can be
localized according to the d band structure, the curve C describes the extreme saturation
process. The ECo, PdMn alloys CORespOIId to the B case, the pdFe, PJCo are in an
intermediate regime. In an enhanced lattice, the charge screening of the impurity (located
mainly in the impurity cell) has a quite different radial dependence than the spin polariza-
tion which is built up at long distances by electron hole excitation.

was recognized experimentally that this minimum must be attributed to the

existence of 3d magnetic impurities. This behaviour has been a theoretical
puzzle as an exchange model leads in second order in J to a resistivity con-
tribution R independent of the temperature,

R, - J z S [ S + 11.
676 J. FLOUQUET [CH.9, 8 2

The theoretical explanation was given in 1964 by Kondo who showed that a
logT contribution occurs if we take into account the third power of J in the
perturbation :

The resistivity minimum appears as a characteristic of an antiferromagnetic

coupling (J > 0) which leads to a logarithmic increase of the resistivity at
low temperature. Abrikosov (1965) has shown that higher order in the
perturbation must be taken into account when the temperature decreases.
Below a characteristic temperature defined by

the coupling between the conduction electrons and the localized moment
becomes so strong that a perturbation calculation breaks down. The impurity
seems to be described by two regimes:
(i) a weak coupling regime (T > TK)where the impurity carries a well-
defined moment;
(ii) a strong coupling regime (T < TK) where the roles of the conduction
electrons cannot be described by a HF approximation.
In the weak coupling region, the principal role of the resonant coupling J
is to give rise to dynamic effects in which the conduction electrons are
scattered from the impurity without a strong correlation effect. Thus, locally,
on the impurity site, the conduction electrons are limited to providing a
reservoir which produces relaxation of the spin S whereas the occupation
of the state I S, S,) is practically determined by their unperturbed energies.
For the case of S = 4 (the only case studied theoretically below TK), the
ensemble (impurity-conductionelectrons) is well described by the degenerate
non-perturbed state,

where xa represents the two states of S, and *v the Fermi sea without
electron-hole excitation.
In the strong coupling region, by contrast, we no longer have a simple
relaxation process, but rather a correlation between the impurity spin and
that of the scattered electrons which means that the scattering of a second
electron depends on the spin of the first. The low temperature singlet state
CH.9, 5 21 METALS WITH MAGNETIC IMPURITIES 677

theory indicates that as T + 0 the combined state @ tends toward a singlet

of the type (Yosida and Yoshimori 1973)

where ll/u schematically represents the combination of electrons of spin o

with a hole of spin-o. The fluctuation between the two states +$ is no longer
controlled by the thermal energy kBT but by the coupling energy kBT'.
Experimentally if the susceptibility can be fitted by a Curie-Weiss law in a
certain range of the ratio TIT,,

it is well known that the 6 value depends on the experimental range of

temperature.
We will discuss briefly the present theoretical situation and describe the
temperature dependence of the susceptibility. As the limit of the weak
coupling is well described, the two main points are to obtain an exact
solution (i) for the strong coupling case, and (ii) in the cross-over regime.

2.2.2. Low temperature solution

Using scaling theory, Wilson (1974) has shown that two stable points in
J space describe at OK the solution of the ferromagnetic and antiferro-
magnetic cases: these fixed points are respectively J = 0 and J = + co.
><
The fundamental states of both cases (J 0) are completely different: for
J c 0 the impurity is strongly magnetic and its susceptibility diverges at
0 K, while for J > 0 the ground state must be a singlet (J -+ + 00) and the
susceptibility is constant at 0 K. Wilson reached an exact zero-temperature
solution and made finite temperature corrections.
Nozi6res (1974) has shown that, in the strong coupling limit (T c TK),
the low temperature properties can be derived phenomenologically in the
same spirit as in the usual Landau theory of Fermi liquids. Because the singlet
remains somewhat polarizable an indirect repulsive interaction between
electrons of antiparallel spin occurs. This interaction leads to a zero-
temperature susceptibility
678 J. FLOUQUET [CH. 9, 6 2

As in the Pauli susceptibility of a metal (TF-+ TK),the low temperature

excitations give only a quadratic deviation in T.
Recently Yamada (1975) and Yosida and Yamada (1975), investigating
the Anderson Hamiltonian with electron-hole symmetry (eq. (2.1) :
Ed = -3U+EF, the so-called symmetrical Anderson model, E, = -3U)
by a perturbation expansion in a power series of the Coulomb energy U
have: (i) clearly demonstrated the presence of the H F and Kondo mechanism
for the occurrence of magnetism; (ii) proved the Nozi6res Fermi liquid
theory based on the s-d exchange model. Figure 12 represents the density

1.0

0.5

0
0 5 10

Fig. 12. The density of states for the d electron calculated by Yamada for the symmetrical
Anderson Harniltonian (E,, = -)U) using a perturbation expansion in a power series of
the electron correlation U. This calculation shows the reasonable structure in the whole
range of E/A including the large U limit. In the HF magnetic case (U/nA = 2 or 5). the
broad peaks appear near E = +)U. (The F e d energy is taken as the zero energy,
right-hand side are only shown.)

of d states, p d , obtained by Yamada as a function of the relative energy E/A

for various values of q = U/nA, the HF parameter. For strongly H F
magnetic impurities (q > l), three peaks occur: the two located at E, = &+U
describe the HF regime, the third located at the Fermi level represents the
Kondo coupling. The striking result is that for q < 1 only one peak occurs
almost independent of the strength of q. The paramagnetic impurity has a
zero moment. For > 1, the paramagnetic impurity moment is completely
quenched below TKby the Kondo correlation; above TK, the paramagnetic
impurity carries a well-defined moment since the thermal energy averages
CH.9, 8 21 METALS WITH MAONETIC IMPURITIES 679

the sharp peak centered at the Fermi level. The HF transition (q = 1)

shows a broadened Kondo anomaly, the entropy of the magnetic moment
shifts the local moment regime to the U < d region (Friedel 1976). Krishna-
murthy et al. (1975) have schematically represented the different regimes of
the impurity as a function of the three variables T, U,A (fig. 13). The drawn
surfaces describe respectively the planes T = xA, T = U and the cross-over
surfaces T = T,(A, U).As is noted by the authors, in contrast to the drawing,

t T (Temperaturo)

T. nA
plane

T=T, (A#)

A ( d level width) U.mA

Fig. 13. Schematic sketch of the various schemes arising from the susceptibility results
for the symmetric Anderson model. The high temperature free orbital regime has no
physical meaning as the strong coupling limit for U = 0.

the separation between the various regimes is quite fuzzy; notably the
definition of an infinite Kondo temperature for the zero-moment para-
magnetic impurities has no physical meaning.

2.2.3. Finite temperature solution

Finite temperature calculations were made numerically in the cross-over

+
region by Wilson (1974) using an S = exchange Hamiltonian. Figure 14
shows the variation of k,TX1g2& as a function of logT/TK. At high tem-
perature
680 J. FLOUQUET [CH. 9, 8 2

which corresponds to the pure Curie law limit. At zero temperature

If an empirical Curie-Weiss relation is used near OK, one can see that
e =2 . 5 ~ ~ .
Recently numerical calculations performed by Krishnamurthy et al.
(1975) using a symmetrical Anderson model led to the same dependence.

0.25 I I I I I I I

Fig. 14. Universal plot of kBTX(T)/(gPB)' versus logT/TK,where z(T) is the impurity
susceptibilityfor the spin 3 exchange Kondo Hanultonian (Khrishnamurthy et al. 1975).

2.3. INFLUENCEOF THE HYPERFINE COUPLING

This discussion neglects the fact that, a t low temperature, the localized
moment may have a hyperfine coupling with its nucleus,

Two different cases occur, according t o whether the hyperfine coupling is

greater or less than the Kondo coupling.
For k,TK > A, the local moment is strongly coupled to the conduction
electrons, and the appearance of the induced moment on the impurity is
described by the pure electronic term
CH.9, 0 21 METALS WITH MAGNETIC IMPURITIES 68 1

In the full Hamiltonian, the hyperfine term may be regarded as aperturbation;

the spinsIandSare thus uncoupled. The hyperfine coupling can be reduced to

For kBTK< A, the situation is completely different. In low field, the local
moment is strongly coupled to the nuclear spin. We must take the s u m
P = I + S . If the hyperfine coupling is such that a well-isolated ground state I:
can be defined, the Kondo Hamiltonian is only a perturbing term. Its action
on the ground state can be reduced to

where a is defined in table 3 as a function of A (Benoit and Flouquet 1976).

The striking result is that a Kondo coupling may appear or disappear due only
to the action of the hyperfine coupling if I and S are antiferromagnetically
coupled. If the Kondo temperature is defined as a function of the degeneracyn
of the angular momentum (Cornut and Coqblin 1972) by

TK = TFexp+ l / J p n ,

we remark that TKchanges even when Z and S are ferromagneticallycoupled.

Table 3
Variation of the a coefficient of the exchange
Hamiltonian in the electron-nuclear ground
state as a function of the hyperfine coupling
and the electronic and nuclear spin.

AcO A>O

S
- s+ 1
S > I
s+ I s-r+l
S S
s<1 - --
S+I I- s+ 1
S=&
- I
-- 1
s< I 2z+ 1 21+ 1
682 J. FLOUQUET [CH.9, 0 2

In this case, the Kondo temperature as a function of I is

for Z = 0, TK = TF exp [+2/Jp(2S+ l)],

for I # 0. TK = TF exp [2/Jp(2S+S/F)].

As F = I+S > S, the main results are

-
Using Jp(2S+ 1) = 0,068, a typical number for an alloy like AuMn, we get
in the F + 00 limit

When the ground state F is a singlet electron nuclear state (A > 0,

I = S = +), no exchange coupling may occur as long as this ground state
is well isolated. A good example will be given in $ 4 by the -
AuYb study of
the Grenoble Group.

2.4. NO IN THE SINGLE IMPURITY STUDY

We again emphasize that NO experiments have the advantages of permitting

magnetic measurements to be made at low impurity concentrations, including
the observation of the local moment appearance at 0 K without any resonance
condition. The first point is experimentally important if we want to study a
well isolated impurity without any magnetic interaction with the other
impurities.
As the NO signal can be detected only if the impurity is sufficiently
polarized, we are interested in the cases where TK is lower than 10 K. The
low magnetic field study will give the strength of the Kondo coupling beside
the hyperfine coupling, the high magnetic field study will restore the local
moment completely decoupled from the conduction electrons and from the
nuclei so long as H > kBTK/gpB, H > AI/gpB.
The limits A > kBTK,A < kBTKwill be called respectively the weak and
strong Kondo coupling regime. This definition is almost the same as that
used by Wilson and NoziBres, since in NO, A has often the same order of
magnitude as the thermal energy in order to allow an appreciable y ray
CH.9, 4 21 METALS WITH MAGNETIC IMPURITIES 683

anisotropy. The main difference occurs, as was remarked in the last section,
at very low temperatures (Flouquet 1971a; Flouquet and Brewer 1975;
Hartmann 1976).

2.4.1. Weak Kondo coupling regime kBTK6 A

In a first approximation, the main coupling is described by the following

hyperfine Hamiltonian

where gpBHSz , g & f I , are respectively the electronic and the nuclear
Zeeman terms. The NO response, for example the axial anisotropy E(O),
can be computed knowing the electron-nuclear wave function and energy
levels of this full Hamiltonian.
In zero applied field, the different eigenstates are defined by the total
angular momentum F,and their energies are related to A by

EF = +A{F(F+ l)-S(S+l)-l(Z+ 1)).

When the Zeeman terms appear, the component F, is an eigenstate of the

Hamiltonian which can be diagonalized inside each F, value. For high
magnetic fields (gp,H 6 A), the hyperfine coupling can be treated as a
perturbation on the S, electronic states which are well decoupled. Such a
situation is well known in atomic physics when the spin-orbit coupling is
comparable with the applied field; the low and high field limits correspond
to the Zeeman and Paschen Bach effects respectively.
As the two parameters g,p, and Z are assumed to be well known the
theoretical function E:(O) seems to depend on the three parameters A, S, g.
In fact, when the electronic magnetization is completely saturated, the
impurity of spin I sees an effective field equal to

+
Heff(sat)= H H,,(sat),

where &,(sat) is related to A S by the relation

684 J. FLOUQUET [CH. 9, $ 2

As this value is easily obtained in a high field measurement, two paa-r

meters S,g can be chosen. E: is the analogue in NO of the Brillouin function
B: in magnetization experiments. It will be computed for different values
of the applied field and of the temperature.
If one is in the habit of representing NO results in the form of an effective
hyperfine field, one calculates the hyperfine field H: which corresponds to the
theoretical angular distribution E@). Figure 15 compares H i and B; as a

Fig. 15. Comparison of an NO and M response to the free spin Hamiltonian YP,,
[eq. (2.311.

function of the applied field at 10 mK for the special case of a 54Mn probe
which corresponds to the values I = 3, S = 2.5, g = 2, &(sat) = -400 kOe.
For H = 0, the relative splittings between each successive F level are 35, 29
22, 16, 10 (in mK). The smooth variation of H i expresses the weak mixing by
the applied field between each Flevel ; the electronic response reaches rapidly
the Brillouin limit since (i) the Zeeman electronic term is three orders of
magnitude greater than the corresponding nuclear one; (ii) the degeneracy
of the electron nuclear state is rather high (12 for the ground state F = 5.5
at H = 0). Figure 16 shows the H i temperature dependence for different
values of the applied field. Contrary to the behaviour of the Brillouin function,
H; is almost independent of 1/Tfor a constant applied field.
CH. 9, 8 21 METALS WITH MAGNETIC IMPURITIES 685

- H i (kOe) -
Au Mn S . 512 g.2 Hhf.-400k0e
t
H in kOa
400 40

1
200 -

4 0,1
100 -
c
0,03

0 1 I I I
*

The sensitivityof these NO functions to the S determination is rather good

as is shown by table 4 which gives at 10 mK for three different applied fields
the relative variation AE = -E Sof the axial function of the previous
s4Mn probe. As the anisotropy is measured with an accuracy better than
AE = 0.5%, the choice between the two values S, S + $ can be made without
any ambiguity in the weak Kondo coupling regime. fi:, like the Brillouin
function, is sensitive almost solely to the product Sg.

Table 4
NO sensitivity to the electronic spin determination assuming
a g factor equal to 2. At 10 mK, AE(”Mn) = E$+’/’-E2s
for &,(sat) = -400 kOe.

150 9.44 8 6 4.6 3.6

600 14.4 8 5 3.3 2.7
1200 9.5 3.3 1.9 1.2 0.79
686 J. FLOUQUET [CH. 9, 8 2

Finally we mention that this function is defined for a given value of the
nuclear spin and changes appreciably when another isotope with a different
spin is observed: the effective field picture, in the weak Kondo coupling
limit, is nuclear spin-dependent as indicated by table 5 which represents at
10 mK the H i values of the 52Mn,"Mn probe.
The first step in the NO analysis is thus to compare the measured effective
field with the calculated curves H@, T ) . Agreement with a particular curie
indicates that the system is indeed in the weak Kondo coupling region.
Disagreement may indicate either a wrong choice of the constants S and g ,
or that the system is in fact entering the strong coupling region (A 4 kBTK).

Table 5
In the case of S = 9, g = 2, free spin function HOsfor
3ZMnand 54Mn nuclei submitted to a saturation hyper-
fine of -400 kOe.

H (W 20 50 100 200 500

52Mn 45 106 178 253 326
(kOe)
H25'z
54Mn 40 93 158 230 310

2.4.2. Strong Kondo coupling limit kaTK B A

In this case the NO response is described by an effective hyperfine field
proportional to the magnetization and, of course, independent of the probe
nuclear spin [see 9 2.3, eq. (2.3)]. The fundamental difference between the
strong and weak coupling is that, in one region, He,, is proportional to the
magnetization and, in the other, it is not. Usually, the Kondo coupling is
evaluated by the expression

(aHeff/aH)H-+O = R &/3kBONO [see eq. (2*3)i,

where R is the hyperfine ratio between the saturated values AS/g,,pn and
the magnetization.

2.4.3. Cross-over region A N kBTK

The NO response, like the magnetization response, is quite difficult to calcu-
late in the cross-over region as no decoupling between I, S, and s can be
CH.9, 5 21 METALS WITH MAGNETIC IMPURITIES 687

performed. In order to visualize this region, Benoit et al. (1976) have used a
very crude model for the singlet formation. Instead of the N-body Kondo
electronic coupling, they have chosen a simple antiferromagnetic interaction
between two spins S = 3 and K = 3,

K.
2: = 2kBToS*

The effective spin K represents the Kondo behaviour of the conduction

electrons and the Zeeman term is restricted to the S spin in order to simulate
the low polarizability of the conduction electron gas. Here, the magnetization
(m) and NO responses can be computed exactly for a well-defined isotope.
The main result is that, if the low field responses are described in terms of
Curie-Weiss laws with Om, ONO parameters,

-
then eNO is always greater than 8, for kBTo A and tends to Om only in
the strong coupling limit (kBT,,> A). In the cross-over region, the pro-
portionality hypothesis between He,, and m (often made in NO) leads to an
overestimate of T K .

2.4.4. Remarks on the decoupling between Zand S

In a spectroscopic method like the MBssbauer effect (ME) or NMR the

decoupling of I, S is attained through the rapid fluctuation of S with respect
to the nuclear Larmor period 7, (typically h/A). For an electronic relaxa-
tion time T~ < z,, the time evolution of Z is determined by relaxation pro-
cesses and the nucleus is submitted to a hyperfine field proportional to the
impurity magnetization

When zS $ T,, the electronic and nuclear spins are strongly coupled. It
is well known that in zero applied field it is possible to observe in a ME
experiment the free precession of the nucleus and to detect the T~ variation
in the region zS 7, by the line broadening of the MSssbauer spectrum.
N
688 J. FLOUQUET [CH. 9, 8 2

Similar dynamic considerations were previously invoked to describe the

decoupling of I and S in NO. These arguments are conceptually wrong as a
NO experiment is a static measurement. In most cases, the electronic
relaxation effects do not change the nuclear eigenstates and hence the density
matrix which enters in the y anisotropy calculation. In dilute alloys, whatever
the electronic relaxation time of the local moment, in the absence of any
Kondo coupling, the experimental data must fit a free spin function H:.
For a ferromagnetic exchange, whatever the strength of T&, the NO
response must fit a free function H: even in the case of infinite coupling
(T& 4 1 at experimental temperature), our response is described by the
fixed point J = 0. It is a property of the Kondo state that the decoupling
between Z and S occurs for A/kBTK << 1 (limit J --t + 00).

2.5. TKSCALE. EXPERIMENTAL

POSSIBILITIESOF THE DIFFERENTHYPERFINE
METHODS

We comment here on the possibility of observing directly the impurity on

its sites by NMR, ME, NO and compare them as a function of T K .
NMR experiments are easy to perform in high Kondo temperature alloys
(TK > 100 K) since the relaxation time is rather long. Two pieces of informa-
tion are usually extracted: the Knight shift and the relaxation time. One of
the interests of such studies is to discuss the consistency between these two
observables and thus the limitation of the theoretical models in describing
a true physical case (Narath 1973a; see 0 3). As TK decreases, the NMR line
width and its relaxation time increase as the magnitude squared of the
coupling; the impurity nuclear resonances are difficult to observe except for
the special cases of abnormally low hyperfine coupling. At the present time
only the Yb resonance in gold has been observed at low temperatures using
a very strong magnetic field (Folstaedt et al. (1975).
Before 1974, the only possibility of observing directly the low TK impurities
seemed to be provided by radioactive methods which necessitate different
criteria for observation. The basic NMR experiment of Boyce and Slichter
(1974) on CuFe, who resolved five satellite lines from the main Cu host
resonance,has offered the possibility of making specific translated impurity
resonance through the satellites. These satellites correspond to a defined
position in the lattice with a weaker electronic coupling p&) than those of
the impurity itself. The application of this method to the CuFe alloys
(TK 27 K) has given rise to the nice experiment of SkaletoF(1975) on
N
CH. 9, 8 31 METALS WITH MAGNETIC IMPURITIES 689

single crystals and to the first dynamical studies through the Kondo cross-
over (Alloul 1975, 1976).
ME leads (i) only to static information if .r& 4 1: this is always the

static information if we can cross over the region .rS/z, -

situation found for the well-known isotope of 57Fe;(ii) to both dynamic and
1. The first
abnormal Kondo departure of .rS from the well-known Korringa law was
seen in a ME experiment performed by Gonzales and Imbert (1973) on a
-
AuYb alloy.
ESR experiments give theoretical information on the hyperfine structure
and on the impurity relaxation. For 3d elements in normal metals, the
hyperfine structure has never been resolved and direct measurement of the
relaxation time is masked by the bottleneck problem (Hasegawa 1959).
For 4f elements both types of information have been observed since (i) the
J (4f) value is lower than the J (3d) value; (ii) the bottleneck is open for 4f
ions in a non-S state. In most cases, J has a negative sign and a constant
value near 0.1 eV; the main mechanism is the direct atomic exchange (see
Orbach 1975; Orbach et al. 1974).
NO, as ME, cannot give any information in high TKsystems as the experi-
mental signal is too low. We describe in $0 3 and 5 an intermediate situation
(AuCo) where both NO and NMR were performed. In parallel to these
general considerations, practical criteria dictate that only one technique
offers the opportunity for looking at a definite nucleus. For example, the
stable atoms of Ce, having even numbers of nucleons, carry no nuclear
moment; on the other hand, the 137mCeisotope is an excellent NO probe.
We restrict this discussion here, neglecting other methods like muon pre-
cession and angular correlation.

3. The hyperfine field. The origin of magnetism

In high magnetic fields when the magnetic impurity is completely polarized,
NO will give the magnitude of the saturation hyperfine field (&(sat)),
The sign of Hhfcan be obtained, (i) in some cases by following the relative
competition between the applied and the hyperfine fields: when the electronic
moment becomes completely saturated, the sole variable is the applied field;
(ii) by performing anisotropy measurements or low temperature ME;
(iii) by detecting the degree of circular polarization of the y rays. For example,
the positive sign of Hhf at a Co impurity dissolved in palladium was
measured by all four methods.
M
690 J. FLOUQUET [CH. 9, 5 3

I will show that measurements of the saturation hyperfine field and

possibly its sign are relevant to the question of the origin of magnetism. The
discussion is not restricted to the NO values as a better understanding is
obtained by a complete compilation of the data.

3.1, ATOM~C
STRUCTURE AND HYPERFINE FIELDS

The hyperfine interaction between an electron of spin and orbital angular

momenta s, 1 with a nuclear spin I is equal to

The first term, called the contact term, exists only for an s electron as the
delta function indicates. The second and third terms describe respectively
the orbital and dipolar effects. If this Hamiltonian is summed over all the
electronic shells n with a restricted HF approximation (same radial wave
function for eachn shell), an ion like M n Z +in an s state will have no hyperfine
coupling.
Using a spin-dependentradial wave function for the n shell a core polariza-
tion effect in the inner shells leads to a hyperfine field proportional to the
spin S of the unfilled shell,

$"JO) being the wave function of the different shells n at the impurity site.
For 3d ions, H:p is intrinsically negative with a 3d free ion value
Ro = H,d,/gpBSof - 120 kOe per Bohr magneton which is approximately
N

independent of atomic number (Freeman and Watson 1965). The orbital

part, Rorb, depends on the atomic number and increases gradually from a
value of + 180 kOe/pBfor the TiZ+ions to a value of +650 kOe/p, for the
NiZ+ions. For a 3d element, the orbital magnetism term has often a bigger
hyperfine response than the corresponding spin term.
For the 4f shell, more localized than the 3d shell, the hyperfine contribution
is essentially orbital except for the s state ions E t + , G d 3 + where the only
contribution is the 4f core polarization. Table 6 lists the hyperfine value of
the 4f free ions (Kondo 1961).
CH. 9, 6 31 METALS WITH MAGNETIC IMPURITIES 691

Table 6
4f free ion hyperfine field.

4f I Ce3+ Pr3+ NdZ+ Pm3+ Sm3+ Tb3+

3.33 4.33 3.93 3.43 3.14

4f 1 Dy3+ Ho3+ Er3+ Tm3+ Yb3+

5.98 1.46 1.64 4.13 4.12

3.2. 3d HYPERFINEFIELDS

3.2.1. Magnetic impurity. Limitation of the models

Table 7 represents the NO results obtained for different alloys; the results
are summarized by: (i) the Sg determination if a fit to a H: function can be
reached; (ii) the strength of the Kondo coupling given by the Weiss para-
meter 8; (iii) the values of the saturation hyperfine field and magnetization;
(iv) the direct ratio R of these two values in the case of a normal metal host
or the ratio R of the saturation hyperfine field by the local magnetization on
the impurity site for the case of an enhanced matrix like Pd, Pt (see 44).
Table 8 describes the ME results obtained for a "Fe probe, and table 9 the
NMR results on the impurity site; the magnetic impurity examples are those
of MoCo and WCo alloys. Finally, table 10 gives: (i) the NMR results
obtained for M F Fe, Co, Ni ions dissolved in a dilute ferromagnetic alloy
of PdFe 2% (Le Dangh Koi et al. 1976); (ii) the g value of the ferromagnetic
resGance detected by Bagguley et al. (1974).
As tables 7 and 8 show, R generally is negative with an average value of
70 kOe/pB, that (i) the main magnetic part is the spin one; (ii) the resonant
mixing is really an I = 2 coupling between a d localized state and an electron
of well-specifiedpartial wave function I = 2 [an I = 0 electron mixing should
give a strong positive hyperfine contribution (R, MOe)]. N

Both conclusions agree with the Anderson picture that the spin magnetism
is more easily fulfilled than the orbital one. If r describes the exchange 3d
coupling between two electrons in a different m = I, orbital and U the
Coulomb interaction in the symmetrical Anderson Hamiltonian, the two
conditions for magnetism are given (see Coqblin and Blandin 1968) by

(U+If)/nd > 1 and (U-r)/nA > 1

 W
Q
N
Table 7a
NO results on 3d impurities in normal host.

M
Ref.

CuCr 1K > I1201 Williams (1970) Daybell (1969)

- 153 3.0 - 51 Brewer (1974) Vochten (1976)
1 2 - 238 3.2 -74 Williams (1970)
H 2 -242 3.2 -76 Williams (1970) Lutes (1964)
25 mK - 280 3.5 - 80 Campbell (1967) Hirschkoff (1971a)
60 mK Pratt (1969) Manhes (1971) I-'
25 mK Flouquet (1971b)
-
AgMn - 328 Cameron (1966) Mahhes (1971)
4omK - 328 Flouquet (1970b) Hanson (1976)
LuMn 2 2 -400 4.5 - 88 Williams (1968) Manhes (1971)
Lagendijk (1969)
Flouquet (1971a)
120 mK - 170 2.5 - 68 Marsh (1972) Caplin (1972)
280 mK - 188 3.2 - 58 Marsh (1970) Newrock et al. (1971)
Li et al. (1974)
300 mK -180 4.8 - 37.5 Marsh (1972) Collings (1962)
20 mK Taurian (1974)
-400 Thomson (1976)
2K Taurian (1974)

&Co K = +29% Holiday (1970) Boucai (1971)

-
Boysen (1973) Narath (1973b) 8
\o
cQ1
W
CH. 9, 0 31 METALS WITH MAGNETIC IMPURITIES 693

Table 7b
NO results on 3d impurities in an enhanced host.

aMn $ 2 - 360 N - 80 Gallop" (1970) Star (1975)

-400 7.5 Thomson (1975)
$ 3 - 370 (ml = 5pB) Flouquet (1977b)
PAC0 1 2 + 210 11 Gallop. (1970) Bozorth (1961)
l0OmK +200 Flouquet (1977a)
-
PtCo 1.6K -200 3.6 - 100 Gallop (1970) Crangle (1965)

QMn
1.6K
70mK
-210
-360 5.2 -
(ml=2pB) Ali (1974)
-70
(ml= SPB)
Gallop (1970)
Tissier (1972)
Tholence (1976)

a Gallop neglects completely the giant moment occurrence as indicated by the H : fit of
the ZCo results; the E M n experiment was performed in a narrower range of temperature
than that of Flouquet et al. (1976). The apparent discrepancy between the H," functions,
found by Gallop and by Flouquet et al. for the B M n alloy, is certainly due to a difference
in the purity of the sample (see Flouquet et al. 1976b).

Table 8
ME results on Fe" in different non-magnetic host (Kitchens and Taylor 1974).

Cu 27 N -90 2.3 -47 Steiner(1973a) Tholence (1970)

Ag 1.6 -36 -2.2 -16.4 Steiner(1975) Hanson (1976)
Au 0.45 -190 2.2 -86 Steiner(l973b) Tholence (1971)
Mo 1 -112 2.4 -46.5 Maley(1970) WPP (1968)
Perez Ramirez (1977) Amamou (1976)
W 0.43 -75.5 2.4 -31.4 Kitchens(l965)
Pd -311 10 -103 Craig(1972) Bozorth (1961)
(ml = 3 ~ 8 )
Pt -301 6 - 100 Kitchens (1965) Crangle (1965)
(mi = 3pB)

"The ME experiments of Ericson et al. (1970,1971), performed at low temperature, show

clearly that the 'CO impurity is less magnetic than the s7Feimpurity in Pd and Pt matrices
{TK(Co)> T,(Fe)}. In each alloy, the hyperhe field of the Co impurity, which is deduced
in zero field from the ME line intensity, decreases with the impurity concentration, while
the hyperfine field of which is deduced from the line splitting (8 1.2.3), is almost
concentration independent.
694 J. FLOUQUET [CH. 9, 5 3

Table 9
NMR results on impurity sites. [When the Knight shift K is decomposed into
Kd and Kerb, the results agree with the Dworin and Narath analysis (1970I.l

AjV 290 -1.5 -3.1 I .6

A_o + 29
guco + 5.2 Narath (1973)
CuNi + 1.28 -0.3 1.6
gV +0.30 -0.4 0.1
&Cr -0.38 -1.4 1 .o
&lMn -2.01 - 3.5 1.5
SCo 45 -6.8 - 26 Narath (1 976)
-
wco 1.8 -1.4

Table 10
NMR and ESR results of 3d impurities dissolved in a
dilute ferromagnetic alloy of palladium.

Mn -400 0.01 2.12 -

Fe - 300 2.17 -
Co +230 0.15 2.33 +
Ni + 175 0.25 2.45 +

'Hhf, dHhrlHhrdescribe respectively the frequency

and the relative linewidth of the NMR observed on the
impurity dissolved in a ferromagnetic alloy of pdFel%
(Le Dangh Khoi 1976).
'g represents the g values derived from ferromagnetic
resonance in the different alloys pdMn, pdFe, pdCo,
-
PdNi with a content of impurity near 1 % (Bagguley and
Robertson 1974; Alquid et al. 1976).
'The last column describes the cases where skew scat-
tering effects were detected (Senoussi et al. 1976).
CH.9, !j 31 METALS WITH MAGNETIC IMPURITIES 695

As the spin magnetic condition is often just fulfilled, the orbital magnetic
condition is not usually reached for 3d impurities in the Friedel-Anderson
approach. We do not discuss the possible origins of a core polarization
attenuation (for more details the reader can refer to Narath 1973a). But the
-
appearance of an abnormal ratio for AgFe, MoCo, WCo and abnormal
hyperfine sign for PdCo, PdNi must be explained,
In insulators, theCo2+on is known as an ion which often carries an
orbital moment; even if the initial splitting C of the crystal field gives a
singlet orbital ground state, the spin orbit coupling (AJ5.S)leads to an orbital
part in the ground state which appears rigidly coupled with the initial spin
part; an induced Van Vleck contribution independent of the temperature
is provided by the applied field mixing among crystal field levels.

1.6
1.4
';;; 1.2
g 1.0
I
Q 0.8
I
0.6

0.4

0.2
r
0 I l l l l l l l l l l l l
0 20 40 60 80 100 120 140
H (kOe)
Fig. 17. Magnetic field dependence of low temperature 59C0resonance shifts in 0.1 at
% WCo. The solid lines are smooth crystal field fits to the data (Narath 1976).

Narath (1976) has interpreted the NMR results of Ws9C0 (fig. 17) in a
pure ionic model with a T z orbital singlet ground s&e and crystal field
excited levels. The small hyperfine field which varies in temperature is attri-
buted to a spin-orbit induced orbital contribution in the ground state; the
temperature-independent Knight shifts, which appear in high magnetic
fields, are attributed to the local moment Van Vleck susceptibility. Assuming
a spin-orbit equal to 0.02 eV, from these two hyperfine values a consistent
crystal field splitting, C = 0.5 eV is obtained. The same analysis for the
696 J. FLOUQUET [CH. 9, 8 3

hyperfine field of Co in Pd can be made assuming a T z spin contribution of

3 pB and an orbital contribution, given by

with Rorb= 500 kOe/p,, Rspin= - 100 kOe/pB, equal to 1 p B . Careful

studies on the CuFe NMR satellites by Boyce and Slichter (1975) are inter-
preted taking into account the crystal field and the energy level parameters.
The values of the crystal field splitting C derived for these three examples are:

-
WCo -
PdCo CuFe
-
C(eV) 0.5 0.2 0.5

-
Although these values have the same order of magnitude as the width A of
the virtual bound state (Asd 0.5 eV), the observation of the crystal field
structure does not contradict the Friedel approach. C and A correspond to
two different mechanisms: (i) C describes an excitation inside the d level;
(ii) A a transfer of a d electron to the Fermi sea. Clearly, d correlation factors
must be incorporated in the Friedel-Anderson treatment which neglects
intra-atomic correlations.
Hirst (1971, 1974) has derived a simple criterion for the observation of a
crystal field structure in the extreme case of strong intra-atomic correlations
with respect to the k-d mixing, as in this situation the impurity must be
stabilized in a well-defined configuration 3d" with n fixed: the splitting of an
intra-configuration is seen if its energy (for example C ) is lower than the
energy of excitation, E,,, to an upper nf 1 interconfiguration. The main
problem for the 3d impurities is that the criterion of applicability, defined as
-
E,, > A , is generally not fulfilled due to the large value of A ( A 0.5 eV).
This difficulty appears when Hirst (1971) attempts to fit the 3d hyperfine
field in a pure ionic approach because such fitting requires the assumption of
two somewhat dubious hypotheses: an abnormally high strength of the direct
coupling and an attenuation of the orbital coupling. A correct description of
the 3d magnetic impurities lies between the ionic and the Friedel-Anderson
model.

3.2.2. Non-magnetic impurity

Table 9 which represents the NMR results, mainly for non-magnetic

impurities, gives the Knight shift values decomposed into an orbital and spin
CH. 9, 31 METALS WITH MAGNETIC IMF'URITIES 697

term according to the Dworin and Narath (1970) calculation which has shown
that, in the non-magnetic regime, the orbital susceptibility has an important
contribution given by the following expressions

4&21+ 1) 2&(21+ 1)
Xorb = , Xspin =
nkBTsfl nkBTsf2 '
where the two characteristic temperatures T,, are linked to the magnetism
conditions by

These expressions show: (i) that for r = 0, xorb- 2xspin;(ii) that Tsfl is
always lower than Tsfl.If the T,, are understood to be fluctuation tempera-
tures, these expressions suggest that the spin and orbital parts fluctuate with
two different parameters. Spin-orbit coupling may mix the different modes.
The striking results of table 9 is that the Dw6rin and Narath analysis can
be made only for the impurities far from the HF magnetic transition. Near
the HF instability, the AuCo studies show (i) an important orbital con-
=
tribution (K k0.3); (ii)he impossibility of treating the orbital and spin
magnetism independently. For the less magnetic AuNi case, Dwarin and
Narath (1970) have interpreted the results by the supplementary assumption
of a crystal field splitting C = 0.2eV. The hypefine properties reflect the
continuity which occurs at the HF instability.
The actual studies performed on 3d impurities show that the crystal field
and the spin-orbit coupling must be taken into account even for a 3d magnetic
impurity near the HF instability. Good evidence of this is given not only by
hyperfine measurements but also by transport properties like skew scattering
(see for example the recent experiment of Senoussi et al. 1976 on PdFe,
-
PdCo, - PdNi alloys referred to in table 10). We remark finally that the orbital
effect must lead to an orbital ESR g shift. Although the results of the ferro-
magnetic resonance cannot be directly extrapolated to the local state of the
impurity, table 10 shows that the g value seems strongly linked to the orbital
contribution.*
*In ECo, E F e alloys, ferromagnetic ESR leads to g factors respectivelyequal to 2.29,
2.15 (Bagguley et al. 1974). The appearance of an abnormal behaviour for the Co impurity
in platinum seems confirmed by the recent high field magnetizationexperiments of Tissier
(1977 )which show a very high Van Vleck susceptibility proportional to the impurity
concentration. New high field NO experiments in the ferromagnetic alloys would check
the origin of the Van Vleck contribution.
698 J. FLOUQUET [CH. 9, 5 4

3.3. 4f HYPERFINE
FIELDS

For 4f impurities, by contrast, excellent agreement is found between insulator

and alloy values if the crystal field effects are taken into account. All the
hyperfine couplings determined by ESR, ME, NO are in excellent agreement
with the ionic model. Deviations may occur near a valence change
(Lid 1).
Table 11 lists the hyperfine fields measured by NO for different alloys,
and the corresponding crystal field ground state is indicated; well resolved
crystal field structures were observed. The Hirst criterion seems well proved

and E,, -
since, for the 4f impurities, C A 0.02 eV (Coqblin and Blandin 1968)
I eV 3 C.
N N

Table 11
NO results on 4f impurities.

Hr' eNO Hdsat) rb Ref.

(kW

r7 + 560 r7 Flouquet (1971b)

AgYb > 10K Flouquet (1974)
&ce r7 + 560 r7 Flouquet (1970a)
&Eu - 134 S Barclay (1975a)
state
&uTb non-magnetic doublet r3with fust excited level Barclay (1975b)
r7at a splitting of 1 K
&uY b r, pcndetermination r7 Benoit (1974)
kce 100 mK + 560 r, Flouquet (1971b)
g2&ce 4oomK r, Benoit (1973)

As the nuclear moment of 17sYbis unknown and the hyperfine coupling of Yb

in Au is known from the ESR experiment of Tao et al. (1971), the NO experiment
in a high magnetic field leads to the nuclear moment determination (Krane 1972;
Spanjaard 1971;Benoit 1974).
'Hr is a fit to a weak coupling function H,: given by a well-isolated ground
state r of the crystal field levels.
bTis the ground state determination made by a Hr fit or by the value of
Hdsat).

4. Single impurity effects

The examples to be given in this section illustrate the different couplings

defined in 9 2. They were chosen particularly in order to show: (i) the capa-
bility of NO measurements; (ii) the interest of comparative NO and M
CH.9, 8 41 METALS WITH MAGNETIC IMPUFUTIES 699

studies (while the former lead to a local response derived from the value of
the hyperfine coupling and a non-local response from the possible enhance-
ment of the Zeeman electronic term, the M experiments always give a
global response); (iii) the possible extension of the NO results to more
interesting M experiments; (iv) the interconnection between different
measurements which can elucidate the magnetic behaviour.
Points (ii) and (iv) will be used in the study of giant moments (PdMn,
PtCo, PdCo). Point (iii) appears clearly in the recent magnetizationand
&tivG measurements performed in Grenoble on - AuYb alloys, point (iv)
in the connection between magnetism and superconductivity.
We shall not discuss experimental details, but we point out that: (i) for
the PdMn, PdCo, PtCo alloys the specific nature and the dilution of NO
expexments2low the observation of an impurity in very dilute alloys where
the contribution of the residual parasitic impurities dominates; (ii) in Lace
alloys, the magnetic behaviour of the Ce impurities can be observed with a
lattice in a superconducting state so long as most of the lattice parts are in a
normal state; (iii) the NO experiments can be performed on bulk materials
usable for other techniques. For example, for the PdMn, PdCo and AuMn
experiments described here, in order to avoid anydoubtabout the purity
of the samples, magnetization and neutron analysis experiments were per-
formed. Finally we point out that the discrepancy between M and NO
measurementsperformed on the CuMn, AgMn alloys are not due to spurious
effects but have a well-defined interpretation. Contrary to the widespread
view, the NO advantage of a greater dilution probably gives the best value of
the Kondo coupling.

4. I . WEAKKONDOCOUPLING

-
4.1.1. Asimpleexample: AuYb

The AuYb alloy is an excellent example of the weak Kondo coupling limit
( A BTBTK).The existence of a predominant antiferromagnetic coupling is
clearly demonstrated by: (i) a negative ESR g shift (Tao et al. 1971); (ii) a
resistivity minimum (Murani 1973); (iii) a deviation of the electronic relaxa-
tion time T~ from the well-known Korringa law. Figure 18 shows the Mtiss-
bauer results of Gonzales and Imbert (1973). With a pure Korringa law, the
product T T should
~ be a constant at low temperature.
NO experiments (Benoit 1974a) have shown that the 175Ybimpurities
dissolved in gold are well described by the spin function H: using an effective
700 J. FLOUQUET [CH.9, 0 4

ii,
160

140 -
130 -
120 -
110 -
preliminary
100 - Mossbauer
90 - results
80 -
I I
0.6 0.81
I I
2
I
3 4
I I
6 8 10
l l I I
20 30
---+
T Kelvin
Fig. 18. Ionic relaxation rates for AjYb, measured via the MBssbauer line broadening in
the 170Yb spectrum (Gonzales Jimenez and Imbert 1973). Relaxation rates obtained by
ESR are also shown (Tao et al. 1971). The relaxation does not follow a Korringa law but
increases logarithmically at low temperatures as expected from a Kondo anomaly.

a
Yb melted after implantation He,,
-function H r7 spin free
1
-
T
-70 K-'

I I
0 1 ' 2 HinkOe
Fig. 19. The NO resulis for dilute "'Yb in Au host, showing a fit to the free spin
function P 7 .
CH. 9, 0 41 METALS WITH MAGNETIC IMPURITIES 701

spin S = 3, with g and A corresponding to the r7crystal field ground state.

This fit shows that the Kondo coupling is much lower than the hyperfme
coupling (fig. 19). This behaviour must also be observable in an ordinary
magnetization experiment. The element Yb has a number of radioisotopes
some of which lack dipole nuclear moments; the experimental situation is
particularly favourable in that the isotopes 1 7 ' Y b and "jYb have moments
of opposite sign, and furthermore, the former isotope fulfills the conditions
for electron-nuclear singlet coupling (A > 0, S = I = 3). Table 12 lists for
171Yb,173Yb,and 174Ybthe nuclear spin value I, the hyperfme coupling A
and the splitting energy C, between the zero field electron nuclear ground

Table 12
Variation of the nuclear spin, the hyperfine coupling and
the splitting between the electronuclearground state and
the first excited state for different stable isotopes of Yb.

"IYb 173Yb 114yb

I 3 I 0
A (a) 127.8 -35.1 0
CF (a)127.8 105.3 0

state F and the first excited level. Figure 20 represents the hyperfine level of
71Ybas a function of the ratio gpgH/A, fig. 21 the corresponding suscepti-
bility. The residual slope below 20 mK is due to the presence of Yb isotopes
other than 71Yb(Frossati et al. 1976); this observation is no more than the
well-known Breit-Rabi effect in atomic physics. Recently, resistivity measure-
ments made at low temperature (T < 200 mK) by Mignot et al. (1976) show
the breakdown of the Kondo scattering below the formation of the Yb
electron-nuclear singlet (fig. 22).

4.1.2. Observation of an enhanced electronic Zeeman term: The PdMn giant -

moment
Star et a]. (1975) have shown by a magnetizationexperiment that amanganese
impurity dissolved in a Pd lattice carries a giant moment of 7.5 pB. As in
PdFe and PdCo alloys, an important fraction of the magnetization is due to
moments induced on the palladium.
702 J. FLOUQUET [CH. 9, 8 4

1 111 Yb: A
I
.127,8 m"K
I I b
0 1
x=- g C'BH
A ;
Fig. 20. Hypefine level scheme of '"Yb. The dashed lines are the asymptotes of the
mF = 0 levels when x = g p B H / A+ 00.

90.6 */. cnr I c he d

Our results
"Ir'
1I-l - Calculated
0
V 1
50
I
100 1/T ( K - 1 ) .

Fig. 21. Susceptibilityof &"'Yb versus l/T(Frossati et al. 1976).

CH.9, 5 41 METALS WITH MAGNETIC IMPURITES 703

As was emphasized, NO experiments will give: (i) the value of the local
moment on the impurity site by the detection of the saturation hyperfine
field; (ii) the value of the induced electronic polarization which does not
contribute to the hyperfine constant, as it is located outside the impurity site
but contributes to the electronic Zeeman term by an enhancement factor
(1 +a) of the local term.

[ nR .cm

10 50 100 500 1000 5000

T (mK)

Fig. 22. The squares and triangles refer to the &'71Yb resistivity of a 415 at ppm alloy;
circles, 0,to the &17"Yb resistivity of a 396 at ppm alloy (Hebral et al. 1976). The

-
different logarithmic slopes reflect only the presence of parasitic impurities of iron
(CFe Sppm). The important point is the occurrence of a maximum in the Kondo
scattering near the temperature where the singlet electron-nuclear state becomes isolated
from the triplet excited level (fig. 20).

As the saturation hyperfine field &(sat) = -370f 10 kOe is close to

that of -400 kOe measured for the Mn nuclei dissolved in gold, the local
moment m, of the manganese in palladium is close to the value attributed
to Mn impurities in AuMn alloys, which is described as an S state with
S = and g = 2. Locally, the Mn impurity in the enhanced palladium
matrix has the same behaviour as in a normal matrix.
Knowing the saturation hyperfine field, comparison of the experimental
anisotropy with an unenhanced free spin function E:o (S = 5,go = 2) shows
an enhanced electronic term (fig. 23). The experimental value fits, down to
704 J. FLOUQUET [CH. 9, 0 4

10 mK, the enhanced function Ef with S = f,g = 3; g is here only a pheno-

menological parameter which reflects the shift of the local go value (go 2)
by the enhancement factor 1 +a,
-
g = go(l +a)*
Below 10 m K a gradually increasing deviation occurs due to the spin-glass
interaction between the Mn impurities and the parasitic iron impurities (at
a concentration near 3 ppm) (Flouquet et al. 1976).

Fig. 23. 835 keV y ray axial anisotropy of 54Mn dissolved in palladium and gold as a
function of l/Tfor H = 50, 100,200 Oe. The curves represent the correspondingfree spin
value Ej5I2 which does not take into account any possible magnetic enhancement
(Flouquet et al. 1976).

Since with the rather high value of I = 3, the composition of I and S

leads to a free spin function H: which is only sensitive to the product S g ,
the choice of S and g is quite arbitrary using such a fitting. The fixed value
S = $ is in agreement with the linear response theory developed later for the
- results, and the ESR g shift reported now.
PtCo
In the common description of the giant moment, the induced moment M i
is rigidly coupled to the local moment M d . The fundamental question is
how to understand the dynamic behaviour. Alquie et a]. (1976) have
recently performed accurate ESR experiments on a - PdMn alloy; their
three main observations were: (i) an unusually large g factor (g 2.1 in
the bottleneck regime); (ii) an even more unusual g shift (dg 0.6) whenN
-
CH.9, 0 41 METALS WITH MAGNETIC IMPURITIES 705

the bottleneck becomes broken, i.e. when the impurity ESR resonance
becomes decoupled from that of the conduction electron; (iii) a strong
Korringa term for the impurity relaxation time (Tzs lo-” sec at 1 K)N

(fig. 24). If this result confirms qualitatively the existence of a giant

moment, we must not forget that the derived values are given using the
Hasegawa equations which are well established for a normal lattice but
must be reconsidered in the presence of a giant moment; the dynamics
of the giant moment is an open problem.

c
C
J

2
2
f

4200 3700 3200 2700 2200 H i n 0.

Fig. 24. ESR experiments at 1.6 K of Alquie et al. (1976) on a C M n alloy containing
500 ppm of Mn. The (1) signal corresponds to a sample annealed for 10 h at 1300 K; the
ESRg factor is equal to 2.146 (point A). The (2) curves describe the ESR of the same
sample after a scratched surface process; the ESR g factor increases up to 2.58 (point B)
while the linewidth increases from 303 Oe to 653 Oe. The (3) curve describes the ESR
signal obtained after an annealing of the sample (2) for 3 h a t 600 K; the ESR signal reaches
its bottleneck limit g = 2.145 and the linewidth decreases down to 305 Oe. The C point
represents a parasitic cavity signal.

If unsuitable dynamical arguments are used for the decoupling between 1

-
and S i n NO experiments, one sees that the Mn impurity fulfills the condition
for the fast relaxation regime ( 0 2.4) as at 10 mK, zs lo-’ sec is much
shorter than a typical Larmor period zn = 2 x lo-* sec. A NO fitting to a
Brillouin function B;’’ would lead to a considerably stronger signal than the
observed H i t 2 , which is characteristic of weak Kondo coupling.
N
706 J. FLOUQUET [CH. 9, 8 4

4.1.3. Other examples

Figure 23 shows that the AuMn alloys fit the free spin function E;'' above
10 mK. Below 10 mK, the deviation will be interpreted as spin glass behaviour
presumably among the Mn impurities. Such free spin behaviour has been
previously observed by Williams (1968) and by Lagendijk (1969). The weak
coupling situation occurs also for the AuCr alloys (Williams 1970) and for
AuCe, AgCe (Flouquet and Marsh 1 9 7 ~ F l o u q u e1971).
t In these examples
the l o c z e d moments are assumed to be in a well-isolated ground state;
when the splitting C between crystal field levels is comparable to the Zeeman
electronic term, the applied field mixing between the levels must be taken
into account. Such a situation was observed by Barclay et al. (1975) for the
16'Tb isotope dissolved in gold.

4.2. STRONG KONDO

COUPLING CASE

4.2.1. Proportionality between H,,and M

As nodirect comparison has been performed for magnetic impurities in normal

lattices, we can only establish in table 13 that for T, 2 0.3 K good agreement
occurs between the Curie-Weiss Kondo constant measured by NO and M
experiments. For example, the accurate NO experiment performed by Brewer
(1974) on CuCr allows verification of the proportionality law.
-
In the c& of AuCo, where the orbital and spin magnetic contributions
have almost the same weight, a comparison cannot be made with the sus-
ceptibility measurement since each different hyperfine contribution must be
taken into account. The excellent agreement between NMR and NO experi-
ments demonstrates the point that the fast relaxation regime and the strong
Kondo coupling limit give the same result (tables 7-9).

Table 13
Comparison for strong Kondo coupling of the
Curie-Weiss temperature measured by NO and
magnetization results.

CuCr 1 1
ZnMn 0.28 0.35 rt 10
-
PtCo 1.6 1.6
AJzbCe 0.4rt0.1 0.3
CH.9, 8 41 METALS WITH MAGNETIC IMPURITIES 707

4.2.2. The appearance of a giant moment

Older susceptibility measurements show that, in the exchange enhanced Pt

lattice, the Co impurity carries a giant moment of 3 . 6 which ~ ~ can be
decomposed into equal induced (mi) and local parts (md)(Crangle and
Scott 1965). NO experiments by Gallop and Campbell (1968) and extra-
polated susceptibility measurements of Tissier and Tournier (1972) show
that the Co impurity goes through a Kondo transition near 1.6 K.

-
A direct comparison between a magnetization experiment, m = m i + m d ,
and a pure local hyperfine measurement (Herr md) will be re!evant to the
problem of the formation of the induced moment on the matrix sites as a
function of the appearance of the local moment. Ali et al. (1974) have
extended the Gallop NO experiments in fields up to 70 kOe in order to
cover the magnetic field range used by Tissier and Tournier.
The comparison of NO and M is described in fig. 25. The hyperfine
effective field appears to be proportional to the global magnetization up to
the complete development of the local magnetization, which is known to be
proportional to the hyperfine effective field in the strong Kondo coupling
limit: the induced moment on the matrix is then proportional to the local
-
magnetization. The particular advantage of PtCo is to extend the demon-
stration over a very large range of applied fields.
The existence of a Kondo-like state for the larger giant moment of PdCo
( M = 12 pB, TK = 100 mK) (Flouquet et al. 1976a) makes questionabFthe
classical description of a giant moment. Usually these moments are described
by a ferromagnetic exchange coupling between the spins S, s of the impurity
and the conduction electrons.
Taking into account the NO results obtained on PtCo and PdCo alloys
and following Morya’s analysis for the existence of a local moment (1967),
the appearance of magnetism on the Co sites can be summarized in two
steps. Firstly, thelocalmagnetism M,(r,)appears onthe site ro oftheimpurity ;
its HF existence depends on the narrow band d, its Kondo coupling* is
characterized by k,Ti. Secondly we must take into account the long-range
reaction of the lattice. The high density of states of the narrow band d leads:

*The origin of the Kondo-like coupling for the giant moment is an open problem. The
resistivity of ptCo and PdCo alloys shows a logarithmic decrease. Loram et al. (1971) have
discussedthe different possible mechanisms.They have ruled out a sole Kondo scattering
of s electrons from local Co moments; the temperature dependent resistivity may result
from s electron scattering from enhanced spin ffuctuations within the impurity cell (see
Lederer and Mills 1968).
708 J. FLOUQUET [CH.9, 6 4

-150

-1VI"
-
Magnetization deduction
of M, (HI
N.0 experiments
Sample Results

-50 tia! 1
2
3
h

0
0

-!I H (kOe)

Fig. 25. NO results for very dilute E C o (Ali et al. 1974) compared to the extrapolated
magnetized curve of Tissier and Tournier (1972). The magnetization curve is scaled by the
factor 60 kOe/pB,

(i) to a strong local response of the electron gas described by the action of a
fictitious local field h,(ro) which produces a strong spatial polarization M(r)
linked to the lattice susceptibility ~ ( r - r , , )by the relation

(ii) to a decrease of the Kondo temperature T i . The ferromagnetic description

only takes (i) into account. This crude description undervalues the feed-back
process between the Kondo temperature and the strongly correlated electron
gas.
The observed linear response between the induced and local moment for
the PtCo alloy suggests that more generally, the electronic polarization
responds linearly to the local magnetism whatever the strength of the field.
Analogous agreement has been found experimentally by Boyce and Slichter
CH.9, 5 41 METALS WITH MAGNETIC IMPURITIES 709

(1974) and Alloul (1975) on CuFe alloys well below and well above T K ,
where no extra Kondo polarization occurs in the Kondo state (see Ishii 1976).
(It must be noted that a linear response theory may break down for an
enhanced lattice like Pd in the case of a strong giant moment.)
Finally, as the magnetic moment on the Co sites is slowly restored by the
applied field, an attempt can be made to compare the experimental data
with theoretical expressions which described the local moment induced by
the applied field.
Ishii (1970), using a singlet Kondo approach, has given at 0 K the simple
expression

which approaches the saturation following a (TK/H)’ law. Gallop (1969)

has pointed out experimentally that the -
Pt-Co data are fitted well by the
simple function

which approaches saturation with a (TK/H) law. The Gallop picture

corresponds to a simple model in which, in the symmetrical Anderson
Hamiltonian, the spin up and down virtual bound states are shifted by
the applied field symmetrically with respect to the Fermi level by an amount
6 E = d(gpBH/2kBT’. For the AgFe alloy, Steiner et al. (1975) have found
also that the experimentalresultzaturate more slowly than the Ishii formula;
as for PtCo, a satisfactory agreement is found with a resonance level model
(Schot; and Schotte 1975).
Gotze and Schlottman (1974) have derived an ‘exact’ temperature depen-
dence of the magnetization for the special case of a spin S = +,a comparison
with this model is made by Steiner and Hulner (1975) for the AgFe alloy.
If the low field behaviour of the Kondo systems Fe in Cu, A g s u , Mo is
mainly determined by their Kondo temperature, the magnetization in high
fields cannot be scaled by an universal behaviour (Perez Ramirez and
Steiner 1977). For example, if the resonance level model gives a reasonable
fit to the AgFe and CuFe alloys, it cannot fit the data of AuFe and - MoFe
alloys; s p z a l propezes must be taken into account.

4.3. JNTERMEDIATE COUPLING

The results of Campbell (1967) and Flouquet (1971b) yield a value
710 J. FLOUQUET [CH. 9, 9 4

8 N o = 25mK on CuMn and 8NO = 40mK on AgMn. Magnetization

experiments made by Hirschkoff et al. (1971a) on G M n and Doran and
Symko (1975) on AgMn yield respectively 8, = l G K and 8, = OmK.
We note agreementwith the Benoit (1976) statement that, with intermediate
coupling (A kBTK), ONO is larger than 0,. ( 5 2). But the main problem is to
N

know the significance of 8,.

Three mechanisms contribute to the apparent change of the behaviour of
a single impurity in a magnetization experiment performed at very low
temperature. (i) The conduction electrons, which cooperate in the Kondo
coupling, are in a narrow band kBTKnear the Fermi level (fig. 12); if the
concentration of impurities is such that the number of electrons cannot
realize a complete Kondo compensation for each impurity, the Kondo
coupling appears to be reduced (see Gruner and Zawadowski 1974). This
consideration defines a critical concentration, C , , for the strong coupling
regime (C, TK/TF).
N For a CuMn or an AgMn alloy, the critical concentra-
tion, C, 5 ppm, is just around the IowG value used by Hirschkoff et al.
N

and Doran and Symko. (ii) It is well known that the coupling with the other
impurities changes the behaviour of the single impurity and leads to a dis-
tribution of the Kondo coupling (Souletie and Tournier 1971; Tournier
1974). (iii) Finally, the reduction of TKby hyperfine coupling is more notice-
able in the low temperature susceptibility measurements than in the NO
experiments which are performed in higher fields than in susceptibility
experiments. All these three mechanisms are minimized for the reported
NO experiments since the concentration of the impurity is a t least one
order of magnitude lower than in M experiment.
We emphasize here that the agreement between NO and M experiments
is better if the high temperature susceptibility data only are interpreted
following the numerical analysis of Krishnamurthy. For example, for an
-
AgMn alloy, the susceptibility measurement of Manhes (1971) and Hanson
(1976) leads to an extrapolated value 8, = 60mK at OK which is in an
excellent agreement with the NO data.
New measurements would seem interesting in order to understand the
discrepancy between magnetization experiments. In the next section, we will
see a particular example of a strong TK variation as the temperature decreases.

4.4. KONDOCOUPLING. DEGENERACY

OF THE GROUND STATE

-
A more fundamental contradiction seems to occur for the Lace alloys
CH.9, 4 41 METALS WITH MAGNETIC IMPURITES 711

where the NO results give a 8 value near 100 mK and the high temperature M
experiments yield 8 near 27 K (Flouquet 1971; Edelstein 1971).
By incorporating the crystal field in an Anderson model corrected for the
4f impurities, Cornut and Coqblin (1972) have explained this apparent
conflict. The exchange constant J and the degeneracy n of the occupied levels
change when the different excited states of the crystal field become depopu-
lated; the variation of J is related t o the different initial energy Ed between
the crystal field levels. This effect is basically the same as that of the variation
of the Kondo temperature due to hyperfine coupling (42.3); the main
difference is that in the latter case the product Jn has only a smooth variation.
The Lace alloy is, on the contrary, a spectacular example where the para-
metezn and consequently the Kondo temperature varies appreciably with the
crystal field occupancy. Such an anomaly was also explained by De Gennaro
and Borchi (1973) by adding the crystal field effect to the exchange Hamil-
tonian. Benoit (1976) has shown that their procedure requires the definition
of an arbitrary sign for the exchange constant. It is now well established that
the Coqblin and Schrieffer (1969) Hamiltonian is the best description of the
kf mixing. In this Hamiltonian, the mixing is not restricted, as for the exchange
Hamiltonian, to the transition M-M’ = f 1 between M (theZcomponent of
the 4f angular momentum) and M‘ (the corresponding k angular momentum),
but is allowed for all the M-M‘ transitions.
The alloy Lace offers the advantage that the strength of the J coupling
may be changed by varying the experimental conditions under pressure. The
pressure variation of the hyperfine field of cerium in lanthanum is shown in
fig. 26. At low field, the coupling J increases under pressure as reflected in
the decreasing initial slope 6Heff/6H.At high applied field, the curves show
the same &(sat). These results illustrate a situation in which the impurity
well described by the ionic model, shows a strong sensitivity to the resonant
coupling. Benoit et a]. (1974b) deduce, within the framework of a bound 4f
level, the pressure variation of the relative position of the 4f state: SE/A 1 N

as well as the minimum initial position of the bound state E4, > -34.
One often hears the term ‘chemical pressure’ as it seems possible to change
the Kondo temperature by alloying two lattices in which the impurity has
quite different values of TK.Since the Ce impurity is magnetic in lanthanum
and non-magnetic in thorium, the alloy La,Th, - - -,Ce fulfills this condition.
Pena et al. (1977) have performed NO and M experiments on such an alloy
which appears as a very complicated system where the magnetic behaviour
must be interpreted taking into account the local environment of each
impurity.
712 J. FLOUQUET [CH. 9, 04

The supplementary interest of the NO experiment is to give here direct

information on a magnetic impurity in a superconductinglattice. The problem
of the coexistence of magnetism and superconductivity has undergone a
burst of activity since it leads to elucidation of the competition between
Cooper pair formation, responsible for superconductivity, and the pair
breaking which occurs by spin-flip scattering at an impurity site. The
depression of superconductivity by a magnetic impurity has been studied by
Abrikosov and Gorkov (1960) using second order perturbation theory.

P (kbar)
- 2
--o-- 10
-.+,- 2 (after cycling)
L -110 K”
T

20 H(kOe)

Fig. 26. NO curves for @Ce at various’appliedpressures (Benoit et al. 1974). The solid
and dash-dotted curves were taken at 2 kbar before and after cycling to 10 kbar respectively.
All measurements were made on the same sample at high and low pressure.

More recently Zittartz and Miiller-Hartmann (1970) have shown that pair
breakinghas its maximum amplitude when the Kondo temperature approaches
the critical temperature. Striking re-entrant curves of the superconductive
transition T&) as a function of the impurity concentration n may occur.
The magnetic information was obtained mostly by the use of theoretical
expressions relating the magnetism to transport properties of the alloy. The
confirmation by NO of the indirect information obtained by these last
methods supports the validity of the theories. Experimentally the amusing
fact is that the alloy - -
La,Th,-,Ce, which is a complicated case for an NO
and M experiment (Pena et al. 1976), shows a very nice re-entrant super-
conductive depression (Huber et al. 1974).
CH. 9, § 51 METALS WITH MAGNETIC IMPURITIES 713

5. Interaction effects

Interaction effects among magnetic impuritieswere often regarded as parasitic

effects which mask the single impurity behaviour. We shall emphasize here
that the NO sensitivity to the axial alignment of the nuclear spin makes it
possible to distinguish between purely paramagnetic, ferromagnetic and more
complex ordering situations.
Up to now the interactions among the impurities have not been systemati-
cally studied by NO. We present: (i) for the NO specialist the importance of
reversible and irreversible effects; (ii) the possibilities offered by NO
experiments.
A further possibility offered by NO is the observation of magnetism due to
the presence of other impurities. Two specific examples are given: the PtCo
alloy where ferromagnetic pairs form at a distance up to the range ofthe
giant moment and the AuCo where only first neighbour coupling can modify
the single impurity behaviour leading to pair and triplet groups.
Finally, NO experiments on Ce compounds are reported and the occurrence
of a Kondo lattice is discussed.

5.1. MAGNETISM
OF INTERACTIONIMPURITIES

5.1.1. Spin glass

We consider the coupling between impurities which carry a well-defined

moment; this assumes that the Kondo coupling (kBTK) is much weaker than
the exchange interaction coupling kBT, of the localized moment with the
other impurities which is linked to the J constant by the relation

In a normal lattice, the magnetic interaction among the impurities is

characterized by (i) a spatial disorder of the impurities (like in a glass),
(ii) a spin disorder of the directioh of the magnetic moment. As the analogy
with atomic motion in a glass is found mostly in the rearrangement of the
spin direction (the spatial disorder is quenched), the magnetic ordering
below T, is called a spin glass. The isotropic distribution of the magnetic
moment is due to the oscillating Ruddermann-Kittel-like polarization of the
electronic gas; the r - dependence of the polarization gives rise to some kind
of corresponding state at low concentration c: the specific heat C, the
magnetization M and the ordering temperature T, follow simple functions
714 J. FLOUQUET [CH.9, 9 5

of the reduced parameters T/c, H/c (Blandin 1961; Souletie 1968; Souletie
and Tournier 1969).
The occurrence of an interaction coupling is characterized by (i) a change
in the low field magnetization slope aM/aT at T, (Schmitt and Jacobs 1957;
Kouvel 1963; Tholence and Tournier 1974), (ii) a broadened anomaly in
the specific heat, ( 5 ) a remanant magnetization 6, below T, (Owen et al.
1957), (iv) the appearance of well-resolved ME lines (Violet and Borg 1966)
and of an antiferromagnetic-like ESR signal (Owen et al. 1957).
Until 1971, the molecular field models (Blandin and Friedel 1959; Marshall
1960; Klein and Brout 1963) seemed to explain reasonably well the magnetic
behaviour below the transition T, although the quantitative agreement with
N -
low temperature results (x xo, C T)was explained by a non-physical
Ising model. In the Klein and Brout models, all the spins are assumed to be
parallel and antiparallel to a given direction; the exchange coupling of one
spin with the others can be restricted inside a correlation sphere of radius R, ,
which corresponds to a coupling with n, = 2.27 magnetic impurities.
The theoretical interest for this subject reappeared when Cannella (1971)
discovered a sharp cusp in the low frequency initial susceptibility. (The
magnetic anomaly at T, is strongly decreased in higher fields by the occurrence
of remanent effects.) As the sharp cusp in the susceptibility seems to
characterize a well-defined transition, Edwards and Anderson (197s) have
developed a new theoretical model where there is a ground state with the
spin aligned in a defined direction even if each 2 direction appears to be
random. An order parameter q defined as the average of (S;) gives a non-
zero value below T, .
Two different ‘schools’ of thought appear among the experimentalists.
One points out that the occurrence of irreversible effects explains most of
the spin glass properties; the other will prove the occurrence of a phase
transition at T, and regards the irreversible effects as after-effects which can
be related to the existence of a great multiplicity of low-lying metastable
states or to some additional anisotropic interaction neglected in the calcula-
tion of Edwards and Anderson.
For example, previously Kouvel (1963) argued that the slope deviation
aM/aT is not related to a sudden phase transition but to the existence of
irreversible effects due to anisotropic coupling among the spins below T,.
Tournier (1965) has analyzed the irreversible properties with a model described
by Nee1 (1961) in order to explain the properties of fine antiferromagnetic
grains. In this picture, no paramagnetic spins are coupled in a superpara-
magnetic cloud which has a random statistical possibility of carrying an
CH. 9, 51 METALS WITH MAGNETIC IMPURITIES 71 5

uncompensated moment Mualigned along an anisotropic field in zero applied

field; the volume of the cloud is defined by the physical dimension of the
grain. The main point is that a potential barrier,

leads to a strong temperature variation of the transition probability per unit

time ( T i ' ) of an uncompensated moment along one of its direction H a ,

T, = To exp E,/k,T.

For a temperature Tb, called the blocking temperature, the lifetime of

M,(T,) becomes so long compared with the characteristic time of the
measurement that this uncompensated moment appears as blocked and thus
does not contribute to the low field susceptibility(the presence of a cusp and
of a change in slope BMpT in higher magnetization experiment). Taking into
account the different orders of magnitude, Tb is approximately, in a M experi-
ment, equal to

E, = 20kBTb.

Above T,, the grain behaves like a superparamagnetic group which follows
a Curie law. The T, transition corresponds to the higher temperature Tbin
the Ntel-like approach.
In dilute alloys, the observations of (i) the susceptibility cusp, (ii) the
remanent magnetization with a logarithmic time decrease support strongly a
NCel-like picture. Holtzberg et a]. (1976) have recently shown using a crude
molecular field picture that the anisotropic dipolar energy,

3p2(s1W2* r W,
may explain the cloud formation. The size of the cloud results from the
competition between (i) the internal dipolar energy of the cloud, (ii) the

-
exchange energy between the no inner spins and the spins outside the cloud.
Experimental results lead (i) to no 400, independent of the concentration
for one specific system, (ii) to an anisotropy energy equal to

E, M;AdlgLW

where A , represents the width of the distribution of the anisotropy fields

which are produced by the dipolar coupling. The quadratic term Mi repre-
sents the coherent mechanism which creates the macroscopic anisotropy
716 J. FLOUQUET [CH.9, 4 5

inside the cloud. As the dipolar and exchange coupling follow a r - depen-
dence, scaling laws are observed also for the remanent field.
The presence of irreversible effects can be detected in a magnetization
experiment in two different ways. The thermoremanent magnetization
(TRM) corresponds to a procedure where the sample is initially magnetized
in a field above its ordering temperature then cooled through the transition
in the applied field. The field is switched off later. The isothermal remanent
magnetization (IRM) is obtained when H is applied below T, and is then
reduced to zero. According to the Ntel model, in dilute alloys, (i) the IRM
begins by varying as H 2and the TRM as H, (ii) the IRM and TRM satura-
tion a,,(T) are the same at each temperature. The remanent saturation
o,(T) follows the simple scaling law exp( -aT/C).
During the magnetization of a spin glass, two different regimes may be
obtained: (i) For H = HR, the TRM, or,achieves its complete saturation,
ars;each impurity is poorly polarized as the ratio between the applied field,
H and the molecular field, HM= kBTc/gpB,produced by the other inter-
acting impurities, is low at HR (HR/HM 20). (ii) For H $ H,, each
N

localized moment becomes slowly decoupled from the random molecular

field; the saturation magnetization os of each impurity is ,reached with a
linear law in H-' (as (1 -H,/H)). (See theoretically, Larkin 1970;
N

Matho 1976.)
Table 14 represents the magnetic observables measured by Tholence
(1973) in an AuFe alloy containing 0.5 % of Fe. Crude application of scaling
laws will givzhe equivalent values for another impurity dilution.
Table 14
Tholence results on A_e,.oo, (1973).

0.3 360 42 70 1500

arH(0)represents the TRM at zero Kelvin in a magnetic field H, a,,(O)

the corresponding saturation value which is achieved for H 2 H,,.
os(0) represents the saturation magnetization (m) of each impurity.
ars(0),oris given per magnetic atom, E a n d are the mean values of
the N k l model.
no is independent of the concentration.
T,, HM, As, E, HEfollow the scaling linear concentration law.
CH. 9, 8 51 METALS WITH MAGNETIC IMPURITIES 717

If the 'grain' behaviour is now well established the occurrence of a well-

defined transition at T, is an open question and a great puzzle for the
theoreticians (Fischer 1977). We underline that the first properties do not
reject the second one but on the contrary can occur if an interaction coupling
occurs inside the grain. A naive picture seems to be that (i) just above T,,
the alloy is an arrangement of some local ordered moment in a superpara-
magnetic cloud together with some free paramagnetic impurities; (ii) below
T, (assumed the real transition of the alloy), the coherence length Iz among
the spins increases with the ratio T,/T ( A + 00 for T = 0). The observation
of irreversible effects at T = T, is just the manifestation of the fact that
coherence between the spin occurs at T,: the reversible and irreversible effect
appear at the same temperature (the important point (Blandin 1976) is that
no n,, the Brout and Klein percolation number). At 0 K, all the spins
are frozen and the motion of one local spin cannot be independent of the
others (collective excitations).*

5.1.2. Influence of the hyperjne structures

According to the discussion of i2.3 and the results of table 3, the strength
of the magnetic interactions must also change appreciably when the electron-
nuclear ground state F is well isolated from the other excited F states
(A > kBT) and when the interaction occurs well below the characteristic
hyperfine coupling (A > kBT,). Without hyperfine coupling the ordering
temperature, T:, is related to the degeneracy of the localized moment by
the factor S(S+ I) [eq. (5.1)].
For a well-isolated electron-nuclear ground state, the ordering temperature
T: must be evaluated taking into account the F degeneracy and the change of
the apparent exchange constant (table 3). For a ferromagnetic coupling
(A < 0),T,' is related to T," by the expression
Tf S Z+S+1
-=- X- < 1.
T," I+S S+1

For S = +, this ratio reaches the limit 0.33 for large value of I.

*In parallel to a microscopic observation of the dipolar influence, important studies are
the dynamic observations just around and far below To. The results of Murnick et al.
(1975), McLaughlin and Alloul (1977) and Levitt and Waldstedt (1977), seem to confirm:
(i) a strong variation of the coherencelength below T,; (ii) a complete freezing of the spins
at 0 K (these conclusions are in excellent agreement with the Massbauer experiment of
Violet and Borg 1966).
718 J. FLOUQUET [CH.9, 8 5

For an antiferromagnetic coupling, the two situation S >< Z lead to a

decrease of T,. For S = +,the interaction vanishes for I = 3 and the ratio
reaches the limit 0.33 for Z 4 00.

5.1.3. Appearance of magnetism by the presence of other impurities

In the cases discussed in the last section, the impurities carry their full
moment. If an isolated impurity appears as non-magnetic (T < TK),the
presence of other impurities may modify the behaviour of the single impurity.
Caroli (1967) has shown, using an Anderson model, that two impurities at a
distance r modify their energy position in the Fermi sea and the width of
their virtual bound states according to a change 8pd(EF)of the d density of
st at es,

(#1is a virtual bound state parameter). As this quantity will be positive or

negative, it will be expected for long distances that there will be an equal
probability of increasing or decreasing the impurity magnetism (Tournier
1974).
Magnetization experiments have clearly shown the existence of ferro-
magnetic pairs, antiferromagnetic pairs are not directly detected as the pairs
appear as non-magnetic. Good examples are given in - - by a Cz
CuFe, AuFe
magnetic contribution which can be detected down to temperatures as low as
TK/3000.(Tholence and Tournier 1970; Hirschkoff et al. 1971b; Frossati
et al. 1976c.)
This discussion neglects the influence of the spin polarization. At relatively
high concentrations it is well known that the molecular field HM created by
the surroundings can induce a magnetic moment initially blocked by a
Kondo coupling. For a strongly enhanced matrix like Pd or Pt, the inter-
action of pair impurities will be restricted mainly to the ferromagnetic range A
of their spin polarization since (i) the giant moment can be regarded as a
large scattering centre of radius r = A with a low electronic and spin polariza-
tion outside their giant moment range L; (ii) the complex Fermi surface
leads to destructive interference of the spin and electronic polarization.
Finally in a first neighbour coupling depending on the sign of the electronic
- or antiferromagnetic pairs
response, ferromagnetic pairs or triplets (AuCo)
-
(AuV) may occur.
CH. 9, 5 51 METALS WITH MAGNETIC IMPURITIES 719

OF NO TO INTERACTION EFFECTS
5.2. SENSITIVITY

5.2.1. High sensitivity of the NO experiments to any local misalignment

In order to show the NO sensitivity to any misalignment (2,fi) between

the local axis 2 of quantization and the macroscopic i? axis defined by the
applied field, we have drawn for different temperatures in fig. 27 the axial
response H,,,(O) of a 6oCo nucleus submitted to a hyperfine coupling
Hhf = - 200 kOe along a 2 axis which forms an angle 0 with the axis of the
counter. Although the corresponding magnetization response along H
given by

M~ = s cOS e, s H,,~,

is independent of the temperature, the NO response depends strongly on the

temperature as suggested by figs. 3-6. Assuming a constant angle of mis-

Fig. 27. Influence of a misalignment angle. He,, describes at different temperatures the
6oCoNO response to a misalignment 0 between the macroscopic axis, defined by the
appliedfield, and the local axis 2 of quantizationof the Co nuclei, submitted to a hyperfine
coupling of Hbl= 200 kOe (Taurian 1974).
720 J. PLOUQUET [CH.9, Q 5

alignment (defined by a vertical line), we observe that the effective field

response leads to a decrease of Hefras the temperature decreases (fig. 27).
We have already pointed out that for a single impurity behaviour, the
two regimes A 2 keTKare described by an effective field which is independent
of the temperature. The above arguments show that when the symmetry of the
external field breaks down locally, striking results appear in the temperature
dependence of the effective field. NO is thus an excellent test of an eventual
local breakdown of the macroscopic symmetry defined by H.

5.2.2. Low sensitivity to a site decomposition

In a concentrated alloy, different types of sites may occur; their resolution is
poor by NO which is an integral method. For example, if 6oCo nuclei in
equal proportion are respectively submitted to a hyperfine coupling of
-200 kOe and - 120 kOe along the same 2 axis, without special caution,
the experimentalist associates an unique effective field He,, to the measured
anisotropy which is the average of that produced by each class of impurity.
Between 20 and 10 mK, the relative variation of 6Heff/He,,is only equal to
4 %; very low temperatures must be achieved to obtain a better resolution.
The discussion can be summarized by underlining that compared with a
magnetization experiment: (i) NO is more sensitive to any misalignment
(2,I?) than to an attenuation of the average magnetization; (ii) NO has
almost the same bad resolution in the decomposition of different sites.
Generally in a concentrated alloy only an analysis of concentration effects
allows the extraction of the magnetic behaviour of different sites.

5.3. SPINGLASS BEHAVIOUR IN A NO EXPERIMENT

5.3.1. The models

The NO experiment performed by Compton (1968) on a A u ~ sample, ~ M ~

shows the characteristic spin glass decrease of Heff(T)(fig-28). As at that
time (1965), the sample was not prepared with special caution, a content C,,,
of the most probable iron parasitic impurity was accidentally dissolved
during the sample preparation.
In order to interpret these experiments, Compton developed a crude model
with the following hypotheses:
(i) the magnetic coupling is described by an isotropic molecular field H,,
CH.9. 8 51 METALS WITH MAGNETIC IMPURITIES 721

"ef f
in kOe

350

300

250

200

Fig. 28. NO Compton results (1968) on a &uS4Mn alloy.

(ii) the electronic spin is blocked along the vector sum H,of the applied
field Hand the molecular field HM.(Its magnetization is completely saturated
along H, .)
(iii) the nuclear local axis of quantization coincides with the vector axis
H,(the nuclei are submitted to their saturation hyperfine field).
The axial anisotropy along H is only an average of the anisotropy of each
nucleus in agreement with its local axis of quantization H,:

where

is given by eq. (1.1). Performing the integration over all the 8 angles, EH
can be simply written
722 J. FLOUQUET [CH. 9, 8 5

where a and A,(a) are respectively the ratio H H / Hand the corresponding
attenuation coefficient. The first two even values are

5 - 3a2 3(1 -a2)’

A , @ ) = --
8 16a

{30(1-~~)’-35(1 -a’)’} 105~~-190~~+81

A&) =
64a 96

Figure 29 describes (the full lines), for a Mn nucleus submitted to a hyper-

fine field of -400 kOe the NO response as a function of different values of
the a parameter in terms of an effective field. As was emphasized for the
H i function, this response will be characteristic of the NO parameters.
The main objections to this model are that: (i) for low values of a(-0),
the hypothesis of an isotropic molecular field HM seems incorrect; (ii) for
a 1, for a certain range of solid angles, H , is too low to achieve the
N

blocking of S ; (iii) in high magnetic fields the direct nuclear Zeeman term

I 100
I
200
I
300
I
f inK”
t

Fig. 29. Theoretical models for a 54Mnprobe dissolved in a spin glass alloy and submitted
to a hyperfine coupling of -200 kOe. The solid lines describe the effective field, computed
in the crude Compton model, for different ratios of H M / H ;the dashed lines represent the
corrected results taking into account the Zeeman nuclear alignment (b = Hhr/H).The
new point is the abnormal decrease of Heti as the temperature decreases.
CH. 9, 8 51 METALS WITH MAGNETIC IMPURITIES 723

must be taken into account, which leads to a nuclear orientation axis different
from the electronic axis and consequently to a lower reduction of the effective
field. Taking into account all these remarks, numerical calculations can be
performed using a maximum angle of disalignment O,,(O < Omax < in)
and a supplementary ratio b equal to H,JH (Taurian 1974). Figure 29
represents (dashed lines) the NO response for b = - 10, H = 40 kOe and
a random distribution of 8.
A more sophisticated isotropic molecular distribution can be used. Table 15
describes the A,, A4 coefficients respectively for an unique molecular field
parameter HM = aH, square wave probability and a Lorentzian distribution
of width A, = aH.

Table 15
The A 2 , A , attenuation coefficients for an unique molecular field HM = aH,a square wave
probability up to HM= aH and a Lorentzian distribution of width A M = aH.

Unique molecular Square probability Lorentzian probability

field
a A2 A4 A2 A4 A2 A4

0.1 0.9900 0.9670 0.9967 0.9889 0.9742 0.9200

0.3 0.91 16 0.7239 0.9703 0.9048 0.8217 0.6388
0.5 0.7630 0.3449 0.9192 0.7584 0.6840 0.4702
0.7 0.5621 0.0142 0.8468 0.5894 0.5807 0.3650
0.9 0.3434 -0.0849 0.7591 0.4452 0.5021 0.2953
1.I 0.1941 -0.0209 0.6678 0.3557 0.4409 0.2466
1.3 0.1311 -0.0083 0.5896 0.2989 0.3923 0.21 1I
1.5 0.0956 -0.0042 0.5259 0.2583 0.3529 0.1843
1.7 0.0731 -0.0023 0.4738 0.2275 0.3206 0.1632
1.9 0.0578 -0.0014 0.4308 0.2034 0.2934 0.1466

As A2(a) and A4(a) follow quite different dependences, the use of two
counters perpendicular and parallel to the applied field will be fruitful in
the study of the molecular field distribution. (The A, and A4 coefficients are
simply related to the axial and equatorial anisotropy by the expressions

The B,U,F, , B4U4F4are known from the paramagnetic behaviour.

124 J. FLOUQUET [CH. 9, 85

5.3.2. Spin glass behaviour

Spin glass behaviour has been previously observed in many NO experiments
as a parasitic effect; we have seen examples for very dilute alloys of PdMn
and AuMn. Similar effects were observed for PdMn and PdMnH,zloys
by TGmson et al. (1975, 1976) and for AuMn alloys by many people who
have attempted to prepare a NO thermGeter (Konter 1976; Hiraki and
Ono 1974). The transition from single impurity effect to spin glass behaviour
is shown on figs. 30 and 31 in the case of very dilute alloys of -
PdFeX6'Co,

Hhf in KOP
b ?
FPCO
C,(pprn) v 7.8
+' 6 4
021.6

0.1 KQ A!&-;, .+ .
I I

Fig. 30. Variation of the hypefine field, Hhl = Heff-H, of 6oCo versus T-*for four
different applied fields (40 000/3000/500/100 Oe). The different lines represent the corre-
sponding mean values (Flouquet et al. 1977).

(E < 1 ppm, x < 100ppm). For the more dilute alloys (x 20 ppm), -=
above 500 Oe, an independent value of Herrwith the temperature and the
concentration describes a single impurity effect from which the Kondo
coupling can be extracted; on the contrary for the alloy of 72 ppm, a spin
glass coupling appears clearly. In this range of concentration, the magnetic
coupling between the impurities is principally located outside the ferro-
magnetic polarization carried by the giant moment. Gallop (1968) had
previously mentioned that such a behaviour occurs up to a critical concentra-
tion, C,= 1000 ppm, which is the concentration where two impurities begin
to interact insidetheir ferromagneticpolarization. The same critical concentra-
tion appears in the ordering temperature T, of the PdFe alloys (Chouteau
and Tournier 1971) for C < C,,T, Cz,and for C, C,,T, C. Similar
N N
CH.9, 8 51 METALS WITH MAGNETIC IMPURITIES 725

conclusions were recently reached by Nagamine et al. (1976) in order to

interpret muon precession experiments.
Recently, Sanchez et al. (1977) have observed the transition from single
impurity to spin glass effects for AgMn alloys and have checked over a
large range of concentration (14 to 3000 ppm) the spin glass behaviour. Their
main observations are that (i) the NO results can be described by the scaling
parameter h = H / c (ii) the best fit is obtained with a Lorentzian distribution
centered at H , = 0 with a width A,/C = 480 kOe%.

W'CO GRpprn

I, 1
+ +
m
. + in K-'
200

Fig. 31. The temperature dependence of the hyperfine field of the 6oCo diluted in a
72 ppm iron sample shows a characteristic spin glass behaviour. The horizontal lines are
the mean values obtained on more dilute samples, fig. 30 (Flouquet et al. 1977).

Similar experiments performed on PtMn* by Benoit et al. (1977a) have

shown that (i) the spin glass behaviouroccurs for a concentration up to 1 %
and the fit by a Lorentzian distribution is obtained with a width
A,/C = 40 kOe% which has an order of magnitude lower than that found
for the AgMn alloys (see 5 5.1.3), (ii) above a concentration of 1%, the
scaling 1
G is not respected and the behaviour of the alloy is mostly a
characteristic of antiferromagnetic short-range interactions between the Mn

*For E M n alloys, the NO characteristic of the single impurity shows a temperature

dependence of Hell(Benoit et al. 1977; Thompson et al. 1977). The transition between the
regimes of the single impurity and the spin glass does not appear directly on the results.

hyperfine coupling through the Kondo condensation (T. -

This unusual behaviour for a cubic lattice can be interpreted as either a variation of the
10 mK) or misalignment
effects due to preferential axis. Further experiments on single crystals are being made.
726 J. FLOUQUET [CH. 9. 85

impurities. Similar conclusions were given by Tholence and Wassermann

(1976) performing magnetization experiments; in the spin glass regime, the
width A, deduced from the NO results is in excellent agreement with that
estimated by Sacli et al. (1974) using their specific heat measurements.
Remanent effects were studied on AgMn and PtMn, PtCo alloys by
Sanchez et al. (1977) and Benoit et aL(1977a). Qualitatively, the thermo-
remanent anisotropy was found to be rather low in good agreement with a
Heisenberg coupling between the spins. Quantitatively, its magnitude
depends strongly on the sample preparation; for example with cold working
procedure, the sign of the gamma ray anisotropy was found to reverse below
a certain critical value of the applied field, this critical value increasing with
increasing Mn concentration. The reversed sign of the anisotropy can be
understood as the indication that locally the electronic spins 'prefer to be'
perpendicular to the applied field as it occurs for an antiferromagnetic
coupling. This behaviour must be further investigated and correlated with
the ESR results which were generally interpreted in a simple antiferro-
magnetic scheme (Owen et al. 1957). On the contrary, for the ferromagnetic
alloy of PtCo strong remanent anisotropy was detected with no reversed
sign (Ben% et al. 1977a).

5.4. APPEARANCE
OF MAGNETISMDUE TO INTERACTIONEFFECTS

5.4.1. A giant moment: -

PtCo

Figure 32 represents the effective field seen by 6oCo nuclei dissolved in

different alloys of PtCo,. For a given magnetic field, the main points are
(i) the increase ofx,,, with concentration, and (ii) the constant value of

coupling occurs. The Co impurity initially isolated with a TK 1.6 K is-

He,, as a function of T(Taurian 1974). They suggest that only ferromagnetic

coupled with the other impurities which interact through their positive
ferromagnetic polarization. As was shown by Tissier and Tournier (1972)
and Costa Ribeiro et al. (1974), at low concentration, pairs within the
critical ferromagnetic range (r 5 A) of the polarization are more magnetic
N

than the single impurity.

A simple picture of the decreasing Kondo tempsrature of the pairs (7'')
can be given in a linear response model. So long as T! > T, the Co moment
is an induced moment aligned along H. Assuming a constant positive value
of the polarization in its ferromagnetic range (fig. a), the amplification
m,/mo of the one impurity magnetism, mo = x0H, can be regarded as the
a.
9. 6 51 METALS WITH MAGNETIC IMPURITIES 727

response to (i) the applied field, and (ii) the molecular field H , produced
by the other impurities located inside the ferromagnetic cloud with a con-
centration Ci,, . The following relations can be written

since the polarization is proportional to the impurity xi and lattice xPr

susceptibility. At low concentration, the Kondo temperature follows a C2
dependence.

I /... ...... . * . . . ..
200

100

0
Y 10 20 30
H (k-
40
L

Fig. 32. Hyperline fields points for more concentrated ptCo samples compared to the
magnetization curve determined by Tissier and Tournier (1972) for the same samples. The
magnetization data were normalized by the same factor as in the fig. 25.

- alloys
5.4.2. First neighbour interactions: AuCo

In the last example, the hyperfme coupling defined by H,,,(sat) has the same
limit whatever value the Kondo temperature has. This phenomenon corre-
sponds to an impurity which is fully magnetic in the HF sense. An interesting
case is the AuCo alloy which is on the borderline of the HF transition.
AlthoughTKfor the single impurity is high (-700 K), the low-temperature
Knight shift is so large (+29 %) that it can be detected in NO and NMR
experiments (Holliday et al. 1971 ; Boysen et al. 1973; Narath and Barharn
728 J. FLOUQUET [CH. 9, 6 5

1973). With such a high Kondo coupling, in a normal host, the magnetism
of the impurity can be modified only by first neighbour interactions which
are well known to be ferromagnetic for the Co impurity (see Moriya 1967).
In order to explain their specific heat and susceptibility results, Boucai
et al. (1971) proposed a model where pair and triplet impurities are sub-
mitted respectively to a Kondo coupling 7’’’ = 20 K and T z ’ = 0 K.
With these strong differences in TK, it seems particularly interesting to have
a direct check of the Friedel-Anderson prediction which suggests a spin
magnetism below the H F instability.
The NO method offers the possibility of such studies which are difficult
to perform here by NMR due to the extreme line broadening for the para-
magnetic impurities and to the possible presence of a quadrupolar broadening
when Co neighbours are present. For the first neighbour antiferromagnetic
coupling of AuV, Narath and Gossard (1969) managed to observe both pair
and single impurity signals by NMR (K“’ = - 1.5%, K(’) = 0.6%).

Table 16
Characteristics of the &Co alloys and their corresponding beta-
particle asymmetries.
Sample preparation

Sample Co conc. Relative concentrations of Co species

No. (at %) CN, CN2 cNj %+
1 0.958 89.09 9.67 1.10 0.14
2 1.901 79.43 16.14 3.46 0.96
3 5.184 52.79 23.86 11.58 11.76
4 11.335 23.61 15.60 11.53 49.26
5 11.335 23.61 15.60 11.53 49.26

Beta-particle asymmetries from concentrated CoAu alloys oriented at

negative) is shown for
low temperature (constant geometry). C o s (Ifh<
comparison.
Sample Co Fraction of Np (cold) H sign
conc. (at %) maw. atoms N
)- (kW (Heft)
11.33 60.8 % 0.9948 f 0.0011 40.0 -
0.9850+0.0040 20.0 -
5.18 23.3% 1.0037+0.00?4 40.0 +
-
1.0006f0.0037 20.0 f
1.901 4.42% 1.0200f0.0017 40.0 +
1 .W62f 0.0020 20.0 +
100 ppm 0 1.0091+0.O004 71.9 +-
3 3 ~ 0 ~ 0.8267+_0.0012 10.0
CH.9, 0 5 ) METALS WITH MAGNETIC IMPURITIES 729

Table 16 represents the results of the fl anisotropy experiment performed

by Boysen et al. (1975) on different alloys. The sign of the hyperfine coupling,
given by that of the B anisotropy, changes from positive to negative when the
number of magnetic triplets increases. Further, by separating the various
contributions of the y anisotropy according to the Boucal analysis a net
negative Knight shift must be attributed to the Co pairs. This constitutes
a direct demonstration in a single alloy system of the increasing dominance
of spin magnetism when TKbecomes increasingly low.

1 co

100

0 10 20 90. 40 50 60 70 H,(kOe)
Fig. 33. Effective (net) hyperfine fields He,, at the nuclei of various Co sites in Co&
(see table 15) derived from pray anisotropy data near T = 15 mK. Errors represent the
scatter among the data points. The dashed line labeled Nlis from Holliday and Weyhmann
(1970) and Boysen et al. (1973). These values were obtained on the assumption of a unique,
concentration independent, and uniaxial Herr for each Co species. The lines have no
theoretical significance and merely indicate linear approximations to the data (Boysen
et al. 1975).

Figure 33 represents the effective field attributed to each class of impurities

(see table 15). The main points are:
(i) of the triplet and quartet atoms does not reach a saturation value
although the Grenoble group claims that the corresponding magnetization
is well saturated in a field of 20 kOe.
(ii) H:f> of the pair atoms does not seem to reach a zero value in zero applied
field as would be expected for an induced moment (TE' = 20K). The
730 J. FLOUQUET [CH. 9, 5 5

temperature dependence of H,$.4 with 1/T shows that some misalignment

occurs in the magnetic triplet (see Boysen et al. 1975; Boysen 1976). Using
the correctedCompton model (§5.3.1), Boysen et al. have derived a molecular
field strength of 30 kOe for the triplet. Figure 33 indicates that the same
strength of internal field parallel to H must be applied to pair atoms in order
to understand the possible occurrence of a spontaneous moment.
For Boysen et a]. (1975), the random molecular field HM characterizes
an interaction coupling among the magnetic triplets which occur below
their ordering temperature. We mention here that the dipolar energy
-
( E r ’ 0.5 K) inside the pair and triplet clusters may giveaninner mechanism
of misalignment. This hypothesis is supported by different striking results
in the Boucai (1971) and Costa Ribeiro et al. (1971) experiments.
The remanent value ar,(0)per magnetic atom of the triplet and quartet
atoms is appreciably higher than that of 0.05 pB previously reported for a
dilute alloy of AuFe. If the Holtzberg et al. (1976) analysis is applied to the
triplet and quartet results, the number no of atoms inside one cloud, defined by

is near the number of atoms which build up each triplet and quartet (no 4).
N

The fundamental question not yet resolved is whether the triplet and quartet
form a well-defined quantum object, with an angular momentum indicating
the low value of no 4 (no n,, the Klein-Brout number). According to
N N

the recent observation by Holtzberg et al. (1976) of a remanent magnetization

for the pair of europium atoms which occur in a dilute sample of
Eu2Sr,,S,,,, the dipolar energy barrier may exist well above the triplet
or quartet ordering temperature. The occurrence of an anisotropic dipolar
potential will lead to an internal spin configuration which minimizes the
exchange and dipolar coupling; the three moments carried by the triplet are
not perfectly parallel to each other but form an angle which minimizes the
total energy of the triplet quantum object.
As in zero field, a pair contribution seems to appear in the nuclear specific
heat experiment of Costa Ribeiro et al. (1971), which can detect only the
occurrence of a spontaneous moment, the quantum pair object itself is
perhaps no. described by a single Kondo parameter Tg’ = 20 K since this
value forbids the presence of a spontaneous moment in zero field; some other
mechanism may be present which leads to some coherence among the Co
atoms and formation of pairs.
CH. 9, 8 6) METALS WITH MAGNETIC IMPURITIES 73 1

5.5. KONDOLATTICE OR MAGNETICORDERING IN CERIUM COMPOUNDS

The cerium intermetallic compounds present generally a Kondo behaviour

at high temperature or a valence instability (Parks 1977). The first cases are
characterized by a high coefficient y of the linear temperature specific heat.
For example, AI,Ce has a y coefficient, equal to 1800mJ/T2, two orders of
magnitude higher than that of Pd. The open question is if at low temperatures
the Ce moments undergo a Kondo lattice or a magnetic ordering (Jullien
et al. 1977).
Benoit et al. (1977b) have recently performed NO experiments on Ce
nuclei of the intermetallic compounds AI,Ce, M2Ce, In,Ce which have y
coefficients equal to 1800, 180, 140 mJ/T2, respectively. In low field, the
N

gamma ray anisotropy has the sign predicted by a magnetic coupling along
the applied field for the N,Ce compound but a reversed sign, characteristic of
an antiferromagnetic-like behaviour, for the other alloys. A1,Ce appears
to be a Kondo lattice (see Andres et al. 1975) as the effective field is linearly
induced by the applied field; the other compounds are ordered but, for A1,Ce
lattices, the average magnetic moment of cerium atoms does not reach its
full ionic value within the crystal field but reaches an intermediate value
defined by the competition of the Kondo effect and of the exchange
field.
NO experiments performed on the intermediate valence compound of
Sn2Ce show that the magnitude and the sign of the gamma ray anisotropy
correspond to a brute force NO mechanism along the applied field (Benoit
et al. 1977b): at low temperatures, the Ce atoms appear non-magnetic as it
occurs for a high Kondo temperature.

6. Other applications

6.1, USEOF NO IN LOW TEMPERATURE PHYSICS

6.1.1. Thermomerry
Below 40mK, NO thermometers are very useful and simple to set up.
Primary thermometry can be performed if (i) all the hyperfine and nuclear
parameters of the probe are well known, and (ii) the chosen alloy is prepared
without parasitic effects.
In a ferromagnetic host like Fe, Ni, Co, these conditions are fulfilled for
the 54Mnand 6oConuclei, the most commonly used as thermometers; the
hyperfine fields of the probes have been determined by conventional NMR
732 J. PLOUQUET [CH.9, 8 6

or NMR/NO methods. Generally, relatively high magnetic fields must be

used in order to be sure that a single axis of alignment can be defined. Even
for single crystals oriented along their easy magnetization axis, fields above
3 and 5 kOe must be applied respectively for the cubic NiMn and FeMn
thermometer. A Co single hexagonal crystal provides the possibility o f e r o
field thermometry (see Lounasmaa 1974 for general references).
The conditions (i) and (ii) cannot be assured for non-magnetic hosts
which are sensitive to long-range disturbances (see $5 1.3.2 and 5). The
main advantage of dilute alloys is their adjustable sensitivity through a
chosen applied field value (Pratt et al. 1971). The alloy must be chosen
mostly to minimize the interactions among the magnetic impurities of the
probe (54Mn)and of the parasitic Fe atoms. Two alloys are suitable: PtMn
which has a very low ordering temperature (T, 0.4% of Mn) (Tho%nce
N

and Wassermann 1976); and CuMn where the Fe atoms have a high Kondo
temperature and so a small i z e n c e on the 54Mn probe. On the other hand
thermometry carried out with an Aus4Mn sample was found to provide
variable results (0 5.3); below 15 m z each sample must be checked with
another thermometer.

6.I .2. Magnetic Kapitza resistance

One of the difficultiesin achieving good thermal contact between a liquid

and a solid is the poor thermal conductance at the interface. At low tem-
perature, the thermal impedance, defined by

where is the power applied to the warm part, S the interface area, 6T the
temperature difference between the two materials, varies generally with a
T - law which is predicted for a phonon conductance.
In 1966, the discovery by Abel et al. that the impedance between the
cerium magnesium nitrate salt and the liquid 3He is an order of magnitude
lower than predicted by the T - 3 formula, led to the suggestion that the
magnetic coupling between a localized moment (the Ce paramagnetic centre)
and the nuclear spin of the liquid gives a more efficient mechanism than the
phonon conductance (Leggett and Vuorio 1970).
In metals such effects were observed later by Avenel et al. (1973) and
analyzed carefully by Mills and Beal Monod (1975). The magnetic conduc-
tivity increases as T-' at low temperature for pure paramagnetic impurities;
CH. 9, 61 METALS WITH MAGNETIC IMPURITIES 733

its influence decreases below the ordering temperature T,among the localized
moments since such a coupling blocks its degree of freedom. In order to
increase the thermal contact between 3He and a dilute alloy, the important
parameters to consider are: (i) a low T,per fraction of impurity which may
allow a rather high content of impurities; (ii) a high value of the magnetic
moment. Some of the most convenient alloys are those with a rare earth
impurity like Gd3+ dissolved in a pure metal (Pd, Au, Ag, Pt) since these
alloys fulfill both conditions. A 3d giant moment fulfills the second condition
but leads unfortunately to stronger interaction effects; the only exception is
- alloys, but unfortunately the existence of a Kondo
-
given by the PtMn
coupling (TK 10 mK) certainly reduces the magneticcontribution below TK.
Recently Klein (1977) has developed pulsed eddy current heating of a
radioactive thin metal foil in contact with 3He/4Hein order to measure the
nuclear spin lattice relaxation of dilute 6oCo in Fe and J4Mn in Au. This
method seems important for the study of Kapitza resistance.

6.2. INNUCLEAR PHYSICS

An excellent example of the interconnection between different fields is

provided by the determination of the 7mCenuclear moment. Its initial
value (p = 0.69 p,) was estimated by adjusting the high temperature value
of the entropy S(T) of the cerium magnesium salt measured in calorimetric
experiments (Hudson and Kaeser 1967, Mess et al. 1969) to the NO value
(Huntziger 1970).
With this value, the saturation hyperfine field (Hhf= 560 kOe), which is
measured for Ce nuclei dissolved in a lanthanum host, does not correspond
to the theoretical value of a r7ground state (630 kOe) by the factorf = 1.12.
This discrepancy was resolved by the accurate calorimetric experiment of
Fisher et al. (1973) which attributed at high temperature a lower entropy
than that previously reported. At low temperature, the correction factor
f = 1.17, which must be applied to the NO temperature scale defined by
-
Huntziger, accounts almost exactly for the discrepancy observed in the Lace
alloy.
The NO study of radioactive impurities was performed in different non-
magnetic hosts in order to obtain pure nuclear information: typical examples
are given by the measurement of the multipole mixing ratio of different
transitions in 56Gd(Uluer et al. 1975) dissolved in a gold lattice. Generally,
one of the nuclear transitions gives directly the parent nuclear parameter BK,
734 J. FLOUQUET [CH. 9, 1 7

the study of the other decays gives the nuclear information on the U,F,
coefficient.
Up t o now, we have considered a simple decay scheme without any dis-
turbance produced in the intermediate levels. The study of Au' 69Yb alloys
has led to spurious effects since (i) thermal reorientation m a y occur in the
intermediate levels, with 36 and 660 nanoseconds lifetime, and (ii) a supple-
mentary attenuation factor may arise in the 36 nanoseconds intermediate
state if that state is not a pure 11, M ) state (Steenberg, 1963). Table 17 gives
the results obtained in three laboratories in terms of the first even integral
attenuation G2 observed for both mechanisms in applied fields close to
5 kOe (G, is defined by E(0) = G2g,CJ,F,B2).

Table 17
Attenuation of the anisotropy of the 198 keV gamma
ray emitted by the lS9Ybnuclei as a function of the
Yb concentration.

10 OOO 0.11 Krane et al. (1972)

50 0.20 Pernuk (1976)
<1 0.44 Benoit (1974a)

As this attentuation depmds strongly on the impurity concentration

(difference between the samples of 10 000 and 1 ppm) or on the metallurgical
preparation (difference between the samples of 50 and 1 ppm), important
effects seem to arise from the local symmetry of the surroundings. Table 17
shows clearly the advantage of a great dilution; solid state information was
obtained by Benoit et al. (1974a) using the '"Yb probe which avoids the
existence of auxiliary attenuations.

7. Conclusion
NO studies of dilute alloys have shown that the Kondo coupling occurs as a
general phenomenon for quite different impurities (3d, 4f) and lattices
(normal and enhanced matrix). The interesting nature of the NO study of
localized magnetic states is that the local properties are due partly to non-
localized electron states.
CH. 9.8 7) METALS WITH MAGNETIC IMPURITIES 735

Spin glass studies can be performed by NO. In parallel with magnetiz-

ation experiments, fruitful results could be obtained.
The NO limitation to very low temperatures does not allow the study of
the temperature dependence of the Kondo coupling. Such studies have been
extensively performed by other methods like magnetization, Massbauer
effect, NMR, resistivity, and specific heat. For example, the low temperature
excitation, with a T z term in CuFe, was firstly detected by the specific heat
experiment of Triplet and P h i F p s (1971) using the Maxwell relation to link
the field variation of C to the susceptibility. Such a dependence suggests
that the excitation spectrum of the impurity in a Kondo singlet is like the
Fermi liquid excitation as shown by Nozi6res (1974) and Yoshida and
Yamada (1975). [Such behaviour was previously noticed in NMR results
(Narath 1971).] The Kondo problem seems now resolved for the non realistic
case of a spin one half. The crudeness of such a description appears clearly
when an attempt is made to correlate numerically basic properties like the
specific heat and the susceptibility.
One of the important aspects of the Kondo effect is that it has led experi-
mentalists to consider fundamental questions concerning the significance of
observables. This has, in turn, led to progress in the understanding of the
connection between the measured quantities and the parameters of physical
importance to the theoretician, a connection which earlier often appeared to
be rather tenuous. Similarly, from the purely experimental point of view,
the attempt to study isolated impurities has necessitated a detailed analysis
of impurity interactions and of metal physics problems, and to the critical
evaluation of the possibilities of various experimental methods. For example,
the NMR experimentalist, who attempts to observe a well-defined para-
magnetic impurity through the matrix resonance, is now able to separate
several satellite lines in a CuMn alloy. Figure 34 represents the twelve
- alloy: an unfamiliar picture
satellite lines observed by AllGl(1976)ina CuMn
for a NO experimentalist who can only observe an integral curve with his
technique.
Another important aspect is that stimulation from the Kondo effect work
has led to the performance of a large variety of experiments. The AuYb alloy
is an excellent example. The initial EPR result of Hirst et al. (19%) and the
susceptibility experiments of Gainon et al. (1967) suggested that the - AuYb
alloy may correspond to an antiferromagnetic exchange coupling. Accurate
results were then reported: the EPR shift measurement of Tao et al. (1971),
which proved the negative sign of J, stimulated the Massbauer experiment
of Gonzales and Imbert (1972) which they were later (1973) able to under-
736 J. FLOUQUET [CH.9, 5 7

stand (by the occurrence of a deviation to the ordinary Korringa relaxation

time) following the observation of a resistivity Kondo minimum by Murani
(1973). In order to check the strength of the Kondo coupling, Benoit et al.
(1974a) performed new NO experiments (following Spanjaard et al. 1971)
which have shown (i) the influence of the defects produced during implanta-
tion, and (ii) the weakness of the Kondo coupling. This last effect has

Fig. 34. Satellite resonance in @Mn alloys (Alloul and Hippert 1976).

tempted Frossati et al. (1976b) to perform magnetization experiments

using different isotopes, and Hebral et al. (1976) to observe the resistivity.
With all this physical information, Fert and Friedrich (1974) performed
skew scattering experiments, Follstaedt et al. (1975) observed for the first
time the NMR resonance of a strongly magnetic impurity and Lasjaunias
et al. (1976) have recently carried out nuclear specific heat measurements.
Finally one of the difficulties among physicists is to find a language which
is understood by a non-specialist. It is best for the NO people, in order to
CH.91 METALS WITH MAGNETIC IMPURITIES 737

open their ‘private club’ to show clearly what they measure by (i) drawing
the y ray angular distribution of the observed nuclei, and (ii) quoting the
sensitivity of detection of the different effects (single impurity-interaction-
mixing of a magnetic and quadrupolar interaction).

Acknowledgements
I wish especially to thank Dr W. Brewer, Dr I. A. Campbell, Prof. J. Friedel,
Dr K. Ishii, Dr M. Ribault and Dr J. Souletie for stimulating discussions
particularly during the course of writing this paper. Particularly thanks are
also due to Dr A. Benoit, Dr J. Boysen, Dr J. Sanchez and Dr 0. Taurian
for their collaboration. I have especially benefited from the initial work
performed in Oxford by Dr J. Gallop and Dr I. R. Williams who gave me
the first NO ideas in the Clarendon Laboratory. It is a pleasure to thank
Dr K. Andres, H. Alloul, Prof. A. Blandin, Dr M.Chapellier, Dr B. Coqblin,
Dr P. Monod, Dr J. L. Tholence, Dr D. Thoulouze and Dr R. Tournier for
numerous discussions. I am greatly indebted to Dr Alquie, Dr Alloul and
Dr Mignot for permission to use their unpublished results.

Appendix
Free spin function H i of 54Mn computed for S = 4, g = 2 &(sat) = -400 kOe.
The successive columns give the values of B2,B4,E(O), Herr, 1/T,<&>, <Ix>for seven
values of H ( g 2 = 0.9800 and g4 = 0.9300).

1.44 0.639 0.965 358 1Ooo.o -2.50 - 3.00

1.44 0.638 0.964 358 500.0 -2.50 -2.99
1.43 0.623 0.953 358 333.3 -2.50 -2.99
1.40 0.584 0.924 358 250.0 -2.50 -2.97
1.36 0.528 0.880 358 200.0 -2.50 -2.94
1.30 0.464 0.827 358 166.7 - 2.50 -2.90
1.24 0.401 0.772 358 142.9 - 2.50 -2.85
1.18 0.342 0.717 358 125.0 -2.50 -2.80
1.12 0.296 0.664 358 111.1 - 1.50 -2.75
1.05 0.244 0.614 358 100.0 -2.50 -2.69
0.99 0.205 0.568 358 90.9 -2.50 -2.63
0.93 0.173 0.525 358 83.3 -2.50 -2.57
0.87 0.146 0.486 358 76.9 -2.50 -2.51
0.82 0.123 0.450 358 71.4 -2.50 -2.45
0.77 0.104 0.418 358 66.7 -2.50 -2.39
0.72 0.089 0.388 358 62.5 -2.50 -2.33
0
738 J. FLOUQUET [CH.9

Appendix-Continued

0.67 0.076 0.361 358 58.8 -2.50 -2.27

0.63 0.065 0.336 358 55.6 -2.50 -2.22
0.59 0.055 0.313 358 52.6 -2.50 -2.16
0.56 0.048 0.293 358 50.0 -2.50 -2.11
H - 3000kOe
1.44 0.639 0.965 377 1Ooo.o -2.50 -3.00
1.44 0.638 0.965 377 500.0 -2.50 -2.99
1.43 0.626 0.956 377 333.3 -2.50 -2.99
1.41 0.594 0.931 377 250.0 -2.50 -2.97
1.37 0.544 0.892 377 200.0 -2.49 -2.95
1.32 0.484 0.844 377 166.7 -2.49 -2.91
1.27 0.423 0.793 378 142.9 -2.49 -2.87
1.21 0.365 0.740 378 125.0 -2.49 -2.82
1.15 0.313 0.689 378 111.1 - 2.49 -2.78
1.09 0.266 0.641 378 100.0 -2.49 -2.72
1.03 0.226 0.595 379 90.9 -2.99 -2.67
0.97 0.192 0.563 379 83.3 -2.49 -2.62
0.92 0.163 0.514 379 76.9 -2.49 - 2.56
0.86 0.138 0.479 379 71.4 -2.49 -2.51
0.81 0.118 04 6 380 66.7 -2.49 -2.45
0.77 0.101 0.416 380 62.5 -2.49 -2.40
0.72 0.086 0.388 380 58.8 -2.49 -2.34
0.68 0.074 0.362 380 55.6 -2.49 -2.29
0.64 0.063 0.339 380 52.6 -2.49 -2.24
0.60 0.055 0.318 381 50.0 -2.49 -2.18
H = 0.500 kOe
1.43 0.639 0.965 298 1Ooo.o -2.50 -3.00
1.43 0.634 0.962 298 500.0 -2.49 -2.99
1.41 0.602 0.938 298 333.3 -2.49 -2.98
1.37 0.542 0.891 300 250.0 -2.49 -2.95
1.31 0.468 0.831 302 200.0 -2.49 -2.90
1.24 0.393 0.768 303 166.7 -2.49 -2.85
1.17 0.326 0.706 305 142.9 -2.48 -2.80
1.10 0.267 0.647 307 125.0 -2.85 -2.74
1.03 0.218 0.593 308 111.1 -2.48 -2.68
0.97 0.177 0.544 310 100.0 -2.47 -2.62
0.90 0.144 0.500 311 90.9 -2.47 -2.56
0.84 0.118 0.460 313 83.3 -2.47 -2.50
0.79 0.096 0.423 314 76.9 -2.46 -2.44
0.73 0.079 0.391 315 71.4 -2.46 -2.38
0.68 0.064 0.361 316 66.7 -2.45 -2.32
0.64 0.053 0.334 317 62.5 -2.45 -2.26
0.60 0.044 0.310 317 58.8 -2.45 -2.21
0.56 0.036 0.287 318 55.6 -2.44 -2.15
0.52 0.030 0.267 318 52.6 -2.43 -2.10
0.49 0.025 0.248 318 50.0 - 2.43 -2.04
CH.91 METALS WITH MAGNETIC IMPURITIES 739

Appendix-Continued

H = 0.200kOc
1.44 0.639 0.965 205 10oo.o -2.49 -2.99
1.42 0.607 0.941 205 500.0 -2.49 -2.98
1.35 0.521 0.875 210 333.3 -2.48 -2.93
1.27 0.418 0.790 214 250.0 -2.41 -2.87
1.17 0.325 0.706 218 200.0 -2.45 -2.80
1.08 0.248 0.629 221 166.7 -2.43 -2.72
0.99 0.187 0.560 224 142.9 -2.41 -2.64
0.91 0.141 0.500 227 125.0 -2.40 -2.57
0.83 0.106 0.448 229 111.1 -2.37 -2.49
0.76 0.080 0.402 230 100.0 -2.35 -2.41
0.69 0.061 0.362 232 90.9 -2.33 -2.34
0.63 0.046 0.326 233 83.3 -2.31 -2.26
0.57 0.035 0.294 233 76.9 -2.28 -2.19
0.52 0.026 0.266 233 71.4 -2.26 -2.12
0.47 0.020 0.241 233 66.7 -2.23 - 2.05
0.43 0.015 0.218 233 62.5 -2.21 -1.98
0.39 0.012 0.198 232 58.8 -2.18 -1.92
0.36 0.009 0.179 231 55.6 -2.15 -1.85
0.33 0.007 0.163 229 52.6 -2.127 - 1.79
0.30 0.005 0.148 228 50.0 -2.098 -1.72

H = 0.100kOc

1.43 0.628 0.957 137 10oo.o -2.49 -2.99

1.35 0.513 0.868 137 500.0 -2.47 -2.93
1.21 0.365 0.743 142 333.3 -2.43 -2.83
1.08 0.248 0.628 147 250.0 -2.38 -2.72
0.95 0.165 0.531 151 200.0 -2.33 -2.61
0.83 0.110 0.451 153 166.7 -2.27 -2.49
0.73 0.073 0.386 155 142.9 -2.22 -2.38
0.64 0.049 0.331 157 125.0 -2.16 -2.21
0.56 0.033 0.285 158 111.1 -2.10 -2.16
0.48 0.022 0.246 158 100.0 -2.05 -2.06
0.42 0.015 0.214 158 90.9 -1.99 - 1.96
0.37 0.010 0.185 157 83.3 -1.93 -1.86
0.32 0.007 0.161 156 76.9 - 1.87 -1.77
0.28 0.005 0.141 155 71.4 -1.82 - 1.68
0.25 0.003 0.123 153 66.7 -1.76 -1.60
0.22 0.002 0.108 151 62.5 -1.71 - 1.52
0.19 0.002 0.095 149 58.8 -1.65 -1.44
0.17 0.001 0.08 147 55.6 -1.60 -1.37
0.15 0.001 0.07 145 52.6 - 1.56 - 1.30
0.13 0.Ooo 0.06 142 50.0 - 1.51 -1.23
740 J. FLOUQUET [CH. 9

Appendix-Continued

H = 0.050 kOe
1.38 0.553 0.899 78 10oo.o -2.47 -2.95
1.16 0.315 0.695 85 500.0 -2.37 -2.79
0.94 0.163 0.525 89 333.3 -2.25 -2.59
0.75 0.085 0.402 92 250.0 -2.13 -2.40
0.60 0.045 0.312 93 200.0 -2.00 -2.21
0.48 0.025 0.245 94 166.7 -1.88 -2.03
0.39 0.014 0.195 94 142.9 - 1.78 - 1.87
0.31 0.008 0.157 94 125.0 -1.66 -1.72
0.25 0.005 0.127 93 111.1 - 1.55 -1.58
0.21 0.003 0.104 92 100.0 - 1.46 - 1.46
0.17 0.002 0.086 91 90.0 - 1.38 -1.35
0.14 0.001 0.071 90 83.3 -1.30 - 1.25
0.12 0.Ooo 0.060 89 76.9 -1.23 -1.15
0.10 O.OO0 0.050 87 71.4 -1.16 -1.07
0.08 O.OO0 0.043 85 -1.11 -1.00

H = 0.020 kOe
1.10 0.270 0.648 38 10oo.o -2.31 -2.14
0.67 0.066 0.356 41 500.0 -1.98 -2.30
0.41 0.019 0.210 42 333.3 - 1.66 -1.89
0.26 0.006 0.133 42 250.0 -1.41 -1.57
0.18 0.002 0.089 42 200.0 -1.21 -1.32
0.12 0.001 0.063 42 166.7 - 1.05 -1.13
0.09 O.OO0 0.046 41 142.9 -0.93 -0.98
0.07 O.OO0 0.034 40 125.0 -0.83 -0.86
0.05 O.OO0 0.026 40 111.1 -0.75 -0.77
0.04 O.OO0 0.021 39 100.0 -0.69 -0.69
0.03 O.OO0 0.016 38 90.9 -0.63 -0.62
0.02 O.OO0 0.013 37 83.3 -0.59 -0.56
0.02 O.OO0 0.011 37 76.9 -0.55 -0.51
0.01 0.Ooo 0.009 36 71.4 -0.51 -0.47
0.01 0.Ooo 0.007 35 66.7 -0.48 -0.43
0.01 0.o00 0.006 34 62.5 -0.45 -0.40
0.01 O.OO0 0.005 34 58.8 -0.43 -0.33
0.00 0.Ooo 0.004 33 55.6 -0.40 -0.37
0.00 0.o00 0.004 32 52.6 -0.39 -0.24
0.00 0.Ooo 0.003 31 50.0 -0.37 -0.30
CH. 91 METALS WITH MAGNETIC IMPURITIES 741

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