Z inorg,nucl. Chem., 1975,Vo/. 37, pp 1347-1351. PergamonPress.

Printedin Great Britain

VIBRATIONAL SPECTRA OF SOLID

SOLUTION SERIES WITH ORDERED
PEROVSKITE STRUCTURE
G. BLASSE
Solid State Department,Physical Laboratory, State University of Utrecht, The Netherlands

(Received 2 September 1974)

Abstraet--I.R. and Raman spectra are reported for the following three systems: Ba2CaMo~ xTe~O~,
Ba2_~Sr~MgWO~and Ba2Ca~_~Mg~WO~.In the first series the internal vibrations of the M6+O~octahedra do not
influence each other. The intensity of v~ (MoO~)is five times that of v~ (TeO~). In the second system there is a
gradual, but no linear variation with the composition parameter x. In the third system selection rules are lifted and
new bands appear. Where possible these changes in the spectra are related to the structure of the compositions.

1. INTRODUCTION example. This observation confirms the interpretation of

RECENTLY there has grown interest in the vibrational the higher-frequency bands in the spectra of ordered
spectra of 1:1 ordered perovskites[1-5]. These com- perovskites as internal vibrations of the B'O6 octahedron.
pounds with general formula A2BB'06 offer a unique Similar observations were made for the series
possibility to study the vibrational spectra of B'O6 Ba2CaWl-x Tex 06 [6].
octahedra, if B' is a highly charged caUon
" (I7 + , Mo 6 + , Te 6+, The study of solid solution series of this type makes it
W~+, Nb ~+, SbS÷). This is mainly due to the simple and possible to arrive at a reasonably accurate estimate of the
highly symmetric crystal structure. It has been shown that intensity ratio of the vibrational mode of two different
the vibrational spectra give information on the symmetry B ' O 6 octahedra. In the series Ba2CaMo,_~Te~ 06 the most
of the B'O6 octahedron [1, 2]. For these reasons it seemed striking intensity difference is that for the 121mode of the
interesting to study the vibrational spectra of mixed T e 0 6 and MoO6 group. Figure 1 shows that the
crystals with ordered perovskite structure. The spectra composition with 10% molybdenum shows a Raman
may show the influence of a mixed site occupation and, spectrum with comparable intensity of the v~ mode of the
reversely, the dependence of the spectra on the composi- MoO6 and TeO6 octahedra. By taking integrated inten-
tion of a mixed crystal series may give information on sities we found that vl (MOO6) is five times more intense
structural details of the series. In this work we have than the vl (TeO6). For the ratio between vl (WO6) and v~
considered three series, in which the B', A and B ions are (TeO6) we found this ratio to be about two.
varied, respectively. These are Ba2CaMol-xTexO6, It seems not easy to account for this in a quantitative
Ba2-xSrxMgWO6 and Ba2Cal-xMgxWO6. The deviations way. We can show, however, that the higher intensity for
in the spectra of the mixed compositions from those of the the d o complexes relative to the d 1° complex is not
end members of each series increase in this sequence. unexpected. According to Kettle et al. [7] the intensity of
v~ is proportional with v4(b +2a) ~, where v is the
2. EXPERIIVIENTAL vMrequency and b and a are the bond polarisation
Samples were prepared as described previously[I-3]. They changes along and perpendicular the bond axis, respec-
were checked by X-ray analysis. The vibrational spectra were tively. The lower spectral position of v~ (TeO6) is
measured in the same way as before [1-3]. All measurementswere insufficient to explain the intensity ratio of five. In Ref. [ 1]
performed at room temperature. In the case of Ba2CaMoO6 we argued that the value of a is expected to be larger for
extremely dry KBr has to be used for the pellets, since otherwise the MoO6 octahedron than for the TeO6 octahedron. This
water reacts with the molybdate to give (Ba, Ca)MoO4 and (Ba, explained the low intensity of the v2 mode in the Raman
Ca)(OH):. spectrum of the molybdates and tungstates. At the same
time it can also be responsible for a higher v~ intensity. It
3. RESULTS AND DISCUSSION is impossible, however, to predict in a simple way, how
(a) The system Ba2CaMo~ xTe~O6 the factor b varies from molybdate, tungstate to tellurate.
The series Ba2CaMo~-xTe~O6 shows complete miscibil- Finally we draw attention to the spectra of the end
ity. The vibrational spectra can be described by a member Ba2CaMoO6. Although this compound has been
superposition of the spectra of the end members (x = 0 reported as a cubic perovskite with a = 8.355/~[8], our
and 1). The position of the internal vibrations of the MoO6 spectra reveal that the symmetry of the MoO6 octahedron
and TeO6 group does practically not depend on x. New must be considerably lower than cubic. In Fig. 2 the v3
bands are not induced. This is shown in Fig. 1 for the mode in the i.r. spectrum is shown. For purely cubic
Raman spectrum of Ba2CaMoo~Te0906 as an illustrative symmetry this should be a single mode (symmetry species

1~47
1348 G. BLASSE

Ba2CaMoO6

vl Ba2CaMoO6

.o_

V5

V4

v3 v2

r"
J\ 8 0
I
600
i i
400
v1(Te) .._i-~m~. cm-1
Fig. 2. I.R. spectrum of Ba2CaMoO6 in the Mo-O stretching
i o Ba2CaM°olTeo.906v5 frequencyregion.

(see Fig. 3). The influence of the chemical composition

upon the internal vibrations of the tungstate group is
small. There is a gradual shift in the position of the

3o/
maxima as a function of x and the observed bands are
v2(Te) broader for the solid solutions than for the end members

i i ,
860 660 400 cm-' ?
Fig. 1. Raman spectra of Ba=CaMo06and Ba2CaMoo1Teo.906.

2C
T~,). The spectrum shows, however, that the threefold
degeneracy has been removed completely. Its Raman
spectrum (Fig. I) shows also that the deviation from Oh B.10
symmetry must be considerable, since components of the
v3 and v4 modes (both Ttu and, therefore, forbidden in the
Raman spectrum) are observed in the Raman spectrum.
This is not the case for the corresponding tungstate and 8 4 0 ~ x B.O0
tellurate [1]. Note that this assignment differs slightly from
Ref. [1] and agrees with Ref. [4].
The marked distortion of the MoO6 octahedron in
Ba2CaMoO6 may be due to the fact that the Mo6+ ion is
somewhat too small to fit an octahedral oxygen ion 82(2 790
coordination. This in turn may be related to the
non-existence of a number of molybdates with ordered
perovskite structure, whereas the corresponding tung-
states and tellurates are known[8, 9]. 80C ' 780
O 1 2
(b) The system Ba2-xSrxMgWO6 ----~D-- X
This series also forms a solid solution series for all Fig. 3. Lattice parameter a, position of v, frequency and half
values of x. There is a slight deviation from Vegard's rule width of m, ~v~I2,in the systemBa2-xSrxMgWOt.
 Vibrational spectra of solid solutionseries 1349

(especially in the Raman spectra). The data for v~ in the shows a more extensive splitting than the corresponding
Raman spectra are given in Fig. 3 as an illustrative band for Ba2MgWO6 indicating a larger deviation from
example. We note that the curve of Av~/2vs x is strongly cubic site symmetry for the W6÷ ion in SrMgWO6. We
asymmetric due to the large difference in width of the v, further observed that v2 appears weakly in the Raman
peak in the Raman spectra of Ba2MgWO6and Sr2MgWO6. spectrum of SrzMgWO6(at 590 cm-~), whereas it is absent
This may indicate a larger deviation from complete in the Ba compound. This value agrees with those
crystallographic order in Ba2MgWO6 than in observed by Lentz[4] for other tungstates and may
Sr2MgWO6[10]. The increase of Av~/2for mixed occupa- indicate that the previous assignment of the extremely
tion of the A sites substantiates the arguments used in weak 680 cm 1 band in the Raman spectrum of
Ref.[10] to propose a deviation from complete order in Ba2MgWO6[1] is incorrect. The different intensity of v2
these compounds. indicates that the bonding in the WO6 octahedra of the Sr
It is further noteworthy that the position of the internal and the Ba compound is slightly different.
WO6 vibrational bands is stronger influenced by replacing
Ba in Ba2MgWO6by Sr than by replacing Sr in Sr2MgWO6 (c) The system Ba2Ca~-,Mg, WO6
by Ba (see Fig. 3). The experimental results suggest that This series shows a broad miscibility gap from x is
the non-linearity of the v~ position vs x is connected with about 0.3 to about 0.8. This is probably due to the
the non-linearity of the lattice parameter vs x (Fig. 3). A difference between the ionic radii of Mg~+ and Ca2÷. We
possible explanation may be the following. The Ba note, however, that this broad miscibility gap forms an
compound shows a smaller deviation from cubic sym- exception to the rule of thumb that the (linear) lattice
metry than the Sr compound (see also below). This parameters of isomorphous compounds must differ less
suggests that in the Sr compound there is a larger amount than 5 per cent to have complete miscibility[12]. In the
of cooperative buckling of the corner-shared octahedra present case this difference is only 3.5 per cent. Note that
which enlarges the unit cell[8, 11]. The deviation from Ba2 xSrx MgWO6 where this value is 3 per cent does not
Vegard's rule in the Sr-rich region of the system can then show a miscibility gap. Of all systems described in this
be ascribed to the occurrence of buckling. Introduction of paper the single-phase compositions Ba2Cal-xMg~WO6
Sr in the Ba compound will cause in first approximation a show the strongest influence of a mixed occupation of one
shortening of bond lengths, resulting in an increasing of the crystallographic sites on their spectra.
value of a.o. the v~frequency. At higher Sr concentrations Figure 5 shows Raman spectra of Mg-rich compositions
there will also occur buckling of the octahedra as certainly and Fig. 6 those of Ca-rich compositions. In Fig. 7 the i.r.
is present in the Sr compound. This may influence the v3 band of the end members Ba2MgWO6and Ba2CaWO6is
internal WO6 frequencies less than bond length shorten- compared
ing, resulting in a curve of the type observed experimen- First we consider the magnesium-rich single-phase
tally. region. Inspection of Fig. 5 learns that the replacement of
Finally we compare the spectra of the Sr and the Ba end
members of this series. In Fig. 4 the i.r.-active v3 has been
drawn for both compounds. The v3 band for Sr2MgWO6

Sr2 MgWO 6 Ba2MgWO e /

/ Ba2 Mgo.sCaQ2WO6

ffl

g
5 yk_
%
V1 V 3

i
BOO 700
i i
600
i
500
- - - ~ m l , . ca-1
~
700
i
600 500
.• Ba2MgWO6

Fig. 4. I.R. spectra of Sr2MgWO6 and Ba2MgWO~in the W-O a6o ' 660 4()O :m -1
stretchingfrequency region. Fig. 5. Raman spectra of Ba2MgWO6and Ba2Mgo.sCao.2WO6.
1350 G. BLASSE

octahedron with live Mg2+ ions and one Ca 2÷ ion

(configurations with more Ca 2÷ ions have a considerably
Ba2Cao.75Mgo.25W06 lower concentration in this single-phase region and have
their v, peak probably in the region at somewhat higher
wavenumbers). The 700 cm -~ shoulder in the infrared
spectrum is ascribed to the same complex. Note that the
Ca2+-surrounded WO6 groups have their stretching fre-
quencies at higher wavenumbers than those without Ca2+.
,c This may be due to the fact that the large Ca2÷ ion on a
Mg2÷ lattice site forces the surrounding oxygen ions to
v3 v5 expand so that the W-O distances will shorten resulting in
higher stretching frequencies.

Ba2CaWO6
I
_L A WO6 group with a mixed surroundings does not
posses inversion symmetry as the regular WO6 group in
Ba2MgWO6. Consequently the exclusion principle is not
strictly valid. We therefore assign the weak Raman peaks
800 6C)0 ' 4()0 cm 4
in the region 700-750 cm -~ to components of the v~ mode
Fig. 6. Raman spectra of Ba2CaWO6and Ba2Cao.7~Mg,o 25WO6.
of WO6 groups with mixed surroundings and the weak i.r.
peak around 810 cm -~ to the v~ mode of these groups.
The changes in the Ca-rich single-phase region are less
pronounced. This is shown in Fig. 6 for the Raman
8a2MgWO6 BaaCaWO6
spectra. The v~ peak shifts only slightly to higher
wavenumbers upon introduction of Mg in Ba2CaWOr. At
the same time a new band appears at about 700 cm -1 (see
Fig. 6). In the i.r. spectrum the v3 band shows a slight
broadening. No new bands occur. The Raman band at 700
cm -1 is assigned to v3 due to the absence of inversion
t-
.0
~ V3 symmetry for WO6 octahedra with mixed surroundings.
In Fig. 7 the v3 bands of Ba2MgWO6 and Ba:CaWO6 are
compared. It is clear that the splitting in the case of the
calcium compound is more pronounced than for the
magnesium compound. The former compound will there-
fore show a larger deviation from cubic site symmetry for
\ tungsten. The result of the replacement of Ca in

\ Ba2CaWO6 by Mg may then be a decrease of the amount

of buckling of the octahedra. This can explain the small

700
I 600
I I
500 700
I I
600 500
influence of Mg upon the vibrational spectra of
Ba2CaWO6 in contrast with the influence of Ca upon the
Cl'~"1 spectra of Ba2MgWO6 where bond distances, not bond
angles are influenced. This argument runs parallel with
Fig. 7. I.R. spectra of Ba2MgWO6and Ba~CaWO6in the W-O considerations used above for the system
stretchingfrequency region. Ba2-x Srx MgWOr.

Acknowledgements--The author is greatly indebted to Mr. G. P.

Mg in Ba2MgWO6 by Ca changes the Raman spectrum M. van den Heuvel for the preparation of the samples and the i.r.
drastically: there occur clearly two v~ bands in the region measurements and to Dr. J. H. van der Maas for the measurement
800-850 cm -t and additional new, but weak bands in the of the Raman spectra.
region 700-750 cm -~. The stretching region of the infrared
changes too: the v3 band with a maximum at 610 cm -~ (see REFERENCES
Fig. 7) in the case of Ba2MgWO6 obtains a marked 1. A. F. Corsmit, H. E. Hoefdraad and G. Blasse, J. inorg, nucl.
shoulder at about 700 cm -~, if Mg is replaced by Ca and a Chem. 34, 3401 (1972).
new, weak band appears at about 810 cm -1. These results 2. G. Blasse and A. F. Corsmit, J. Solid State Chem. 6, 513
are interpreted as follows. (1973).
The two Raman v~ lines peak at 815 and 840 cm -~. The 3. J. Th. W. de Hair, A. F. Corsmit and G. Blasse, 3. inorg, nucl.
Chem. 36, 313 (197:4).
former coincides with the v~ peak of Ba2MgWO6 and 4. A. Leutz, Z. Anorg. AUg. Chem. 392, 218 (1972); 402, 153
shows a decreasing intensity with increasing Ca contents. (1973).
It is therefore assigned to the v~ mode of a WO6 5. A. Lentz, J. Phys. Chem. Solids 35, 827 (1974).
octahedron surrounded by six Mg2÷ ions. The 840 cm -~ 6. J. A. Groenink, unpublished results from this laboratory.
peak shows an increasing intensity with increasing Ca 7. S.F.A. Kettle, I. Paul and P. J. Stamper, Inorg. Chim. Acta 7,
contents. It is ascribed to the v, mode of a WO6 11 (1973).
 Vibrational spectra of solid solution series 1351

8. See, e . g . J . B . Goodenough and J. M. Longo, Landolt 10. J. H. G. Bode and A. B. van Oosterhout, to be published.
Bi~rnstein (Edited by K. H. Hellwege), Group III, Vol. 4a, p. 11. H. D. Megaw, Trans. Faraday Soc. A42, 224 (1946).
275. Springer Verlag (Berlin) (1970). 12. See e.g.H. Remy, Lehrbuch derAnorganische Chimie, Band I,
9. G. J. Dirksen, unpublished results from this laboratory. p. 335. Akad. Verlagsgesellschaft, Leipzig (1960).

J.IN.C., Vol, 37, No, 6.--8