Resonating holes vs molecular spin-orbit coupled states in group-5 lacunar spinels

Thorben Petersen1 ,∗ Pritam Bhattacharyya1 , Ulrich K. Rößler1 , and Liviu Hozoi1†

1
Institute for Theoretical Solid State Physics, Leibniz IFW Dresden,
Helmholtzstraße 20, D-01069, Dresden, Germany
(Dated: August 29, 2023)
The valence electronic structure of magnetic centers is one of the factors that determines the
characteristics of a magnet. This may refer to orbital degeneracy, as for jeff = 1/2 Kitaev magnets,
or near-degeneracy, e. g., involving the third and fourth shells in cuprate superconductors. Here we
explore the inner structure of magnetic moments in group-5 lacunar spinels, fascinating materials
featuring multisite magnetic units in the form of tetrahedral tetramers. Our quantum chemical
analysis reveals a very colorful landscape, much richer than the single-electron, single-configuration
arXiv:2301.03392v3 [cond-mat.str-el] 28 Aug 2023

description applied so far to all group-5 GaM4 X8 chalcogenides, and clarifies the basic multiorbital
correlations on M4 tetrahedral clusters: while for V strong correlations yield a wave-function that
can be well described in terms of four V4+ V3+ V3+ V3+ resonant valence structures, for Nb and Ta
a picture of dressed molecular-orbital jeff = 3/2 entities is more appropriate. These internal degrees
of freedom likely shape vibronic couplings, phase transitions, and the magneto-electric properties in
each of these systems.

INTRODUCTION effects across the 3d-4d-5d lacunar-spinel series is miss-

ing, which is the scope of our present quantum chemical
A magnet is a collection of magnetic moments; its cha- study.
racteristic properties are determined by the nature of Besides clarifying essential electronic-structure fea-
those moments and by how they mutually interact. To tures, the multiconfigurational wave-function analysis
shape the properties of magnetic materials according to that we provide — in terms of either localized, site-
specific requirements we therefore need to (i) understand centered or multisite orbitals — makes these materials a
and (ii) have some degree of control over magnetic mo- distinct correlated-electron model system, as illustrative
ments — inner structure and the way they interact with but much more captivating than other platforms typically
each other. It turns out that both — inner morphology employed to illustrate electronic correlations, as e. g., the
and mutual interaction — depend on the subtle interplay H2 molecule for variable interatomic separation [15, 16].
of electronic correlations, spin-orbit couplings (SOCs), Using as indicator for the strength of correlations the
and crystal-field effects (CFEs). The combined action of
these three factors received enormous attention in recent
years. New insights and new ideas in this research area Ga/Al
have led to new physical models, new concepts, and new V/Nb/Ta embedded
S/Se cluster
research paths, as for example Kitaev’s spin model [1]
and extensive associated work [2].
Here we reveal what lies behind effective moments in
Xi
each of the group-5 GaM4 X8 lacunar spinels (M = V,
Nb, Ta and X = S, Se), fascinating materials display-
ing remarkable magnetic [3], magneto-electric [4, 5], and
transport [6, 7] properties. The characteristic structural E
Xo
feature of this family of compounds is that the transition- t2g t2
metal ions are clustered as M4 tetrahedra (see Fig. 1). t2g vs e
The latter can be then viewed as effective (magnetic) electronic a1
sites of a f cc lattice and their electronic structure can be cECP structure t2g t2g
described in terms of Td point-group symmetry-adapted resonating hole molecular orbitals
cluster orbitals — a1 /a2 , e and t1 /t2 . From electronic-
structure calculations based on density functional theory FIG. 1. Lacunar spinel crystal structure and embed-
(DFT), an a21 e4 t12 valence electron configuration was in- ded cluster model employed in this study. From the
ferred [8–10]. While indications of genuine many-body extended solid, a [M4 X28 Ga6 ]25− cluster is cut for quantum
physics are available from both ab initio quantum che- chemical analysis (M = V, Nb, Ta and X = S, Se). Each
transition metal ion M is surrounded by six ligand ions X in
mical investigations [11–13] and dynamical mean field
a distorted octahedron. Xi and Xo labels indicate X atoms
theory (DMFT) [14], an in-depth profile of correlation inside and outside the M4 tetrahedron, respectively, referring
to the basis set assignment in Supplementary Table 2. The
small spheres indicate embedding capped effective core poten-
∗ [email protected] tials (cECPs). Inset: valence level representations analyzed
† [email protected] in this study.
 2

weight of ionic configurations in the ground-state wave- in Td point-group symmetry) contributes with weights
function, we picture (i) what strong correlations mean well below 100% to the ground-state wave-functions; this
in the 3d vanadates (GaV4 S8 , GaV4 Se8 , AlV4 S8 ) and aspect is discussed in detail in the following section.
(ii) the notion of moderate correlations and ‘dressed’ SOC further splits the degenerate 2 T2 components into
jeff = 3/2 objects in the 4d (GaNb4 S8 , GaNb4 Se8 ) and a jeff = 3/2 ground and a jeff = 1/2 excited state in all
5d (GaTa4 Se8 ) variants. Even for the heavier cations, instances, with the magnitude of this splitting increas-
when expressing the multiconfigurational wave-functions ing from 12 meV (3d) to 97 meV (4d) and 345 meV (5d
in terms of delocalized multisite orbitals, the weight of ions); the latter number, in particular, suggests that the
the (...)t12 configuration presently assumed to correctly origin of the peak found at ≈0.3 eV in resonant inelas-
describe the ground state amounts to only 60%. Im- tic X-ray scattering (RIXS) measurements on GaTa4 Se8
pressively, that shrinks to as little as 20% for 3d elec- [20] is spin-orbit splitting within the 2 T2 (a21 e4 t12 ) levels,
trons. Yet, SOCs are still effective — even in the vana- different from the initial interpretation in terms of e4 t12
dates, those give rise to a spin-orbit-induced splitting of → e3 t22 transitions [12, 20].
≈10 meV for the ground-state term. Also peculiar here It is seen that the separation between the ground 2 T
is the near-degeneracy of the ground and a higher-spin and the first excited 4 T state also increases for heavier
state, which should be possible to evidence by either spec- transition-metal species: 41 meV in GaV4 S8 , 475 meV
troscopy or pressure experiments. All these electronic- in GaNb4 Se8 , and 598 meV in GaTa4 Se8 . A denser set
structure features for the 3d case — massive correlations, of low-lying excited state levels in the vanadate could ex-
scaled down but still detectable spin-orbit fine structure, plain the significant deviation from Curie-Weiss behavior
and close proximity of high-spin states — outline a few seen at higher temperatures in susceptibility measure-
important differences between 3d and 4d/5d group-5 la- ments [21, 22], although a quantitative analysis would
cunar spinels, i.e., the starting point in understanding require the inclusion of vibronic couplings and intersite
the differences in their magnetic properties. magnetic interactions (see discussion in Section V of the
Supplementary Information and in our previous work
[12]). The latter then dictate the structure of the in-
RESULTS elastic neutron scattering spectra [23].

High-temperature, tetrahedral-symmetry multiplet

structure. Ground-state correlations in cubic group-5 spinels

The M4 -tetrahedron multiplet structure, as computed A major difference between how the single-tetrahedron
for the high-temperature F 4̄3m cubic lattice arrange- electronic structure is presently depicted in the literature
ment of group-5 lacunar spinels, is displayed in Fig. 2. and in our quantum chemical results is the composition
The multiconfigurational complete active space self- of the ground-state 2 T2 term. Different from the 100%
consistent field (CASSCF) method [17] with an active a21 e4 t12 ground state assumed so far on the basis of DFT
space of seven electrons in twelve orbitals [(7e,12o)-CAS] computations for these materials, we find weights of 72%
was applied. Those orbitals are depicted in Supplemen- in GaTa4 Se8 , 65% in GaNb4 Se8 , and as little as 21%
tary Figure 1. in GaV4 S8 for the a21 e4 t12 configuration. Other configu-
For GaV4 S8 (Fig. 2.(a) ), this (7e,12o)-CASSCF yields rations contributing to the ground-state wave-functions
a high-spin (S = 3/2) ground state. Accounting for dy- imply, for example, double excitations into higher-lying
namical correlation effects in the scheme of post-CASSCF t1 and t2 levels, each of those configurations with a weight
N -electron valence perturbation theory (NEVPT2) [18] of a few percents or even less (see also Supplementary Ta-
corrects this state ordering. Near degeneracy of low- and ble 6).
high-spin states is an effect often seen in 3d systems, due The much more pronounced multiconfigurational char-
to the similar magnitude of Coulomb interactions and acter of the vanadate ground-state wave-function in
various valence level splittings; in solid-state context, the symmetry-adapted orbital basis is also reflected in
a well-known example is LaCoO3 (see [19] for a quan- the correlation index proposed by Ramos-Cordoba et
tum chemical investigation). Spin-crossover effects were al. [15], which serves as a measure for the extent of
also observed in DMFT calculations on GaV4 S8 [14]. In near-degeneracy effects (also referred to as nondynamical
contrast, for the Nb- (Fig. 2(b)) and Ta-based materials correlation in quantum chemistry). Using the (7e,12o)
(Fig. 2(c)), the CASSCF(7e,12o) methodology already CASSCF natural-orbital occupation numbers, we derived
ensures a reasonably good description — the NEVPT2 nondynamical correlation indices IND [15] ranging from
scheme provides only minor corrections to the relative ≈2 in vanadates (1.96 for GaV4 S8 and 2.00 for GaV4 Se8 )
energies in the 4d and 5d systems (see Supplementary to ≈1.05 in the 4d variants (1.05 for GaNb4 S8 and 1.07
Tables 4 and 5). for GaNb4 Se8 ) and 0.92 in GaTa4 Se8 (details are given
While a 2 T2 state is found as ground state in all com- in the Supplementary Table 7). To put this in perspec-
pounds, the a21 e4 t12 electronic configuration (where a1 , tive, along the H2 dissociation curve, IND evolves from
e, and t1 are symmetry-adapted, molecular-like orbitals less than 0.1 at equilibrium distance to 0.5 towards disso-
 3

250 1200 1600

S = 5/2 2
E
S = 3/2 2 2 1400
A 1000 T 2
E
200 S = 1/2 2 2
2 E, A 2
A 1200 2
T 6A
2 A
E 6
A2 2
800 T E 2 A
2
A 1000
Energy (meV)
150 2
A 4
2
T
6 T
A 4
2
T 600 800 T
6
E 4
2
E T 4
T
100 6
A 4
T 600
2 400
A
400 1/2
50 4
T 4
T
200
6 200
E 1/2 1/2
4 2 jeff 3/2 jeff 3/2 2 jeff
T T 2
T T 3/2
0 0 0
CASSCF NEVPT2 SOC CASSCF SOC CASSCF SOC
(a) [V4S28Ga6]25- (b) [Nb4Se28Ga6]25- (c) [Ta4Se28Ga6]25-

FIG. 2. Low-energy multiplet structures for GaV4 S8 , GaNb4 Se8 , and GaTa4 Se8 . The excitation energies were
calculated for (a) [V4 S28 Ga6 ]25 – , (b) [Nb4 Se28 Ga6 ]25 – , and (c) [Ta4 Se28 Ga6 ]25 – embedded clusters (CAS(7e,12o)). Different
spin states S (S = 1/2, 3/2, 5/2) are shown in green, red, and blue, respectively. SOC was accounted for on top of the
CASSCF/NEVPT2 wave-functions. The corrections brought by NEVPT2 are minor for the Nb- and Ta-based compounds and
therefore not depicted (see Supplementary Tables 4 and 5).

ciation [15], although a direct comparison of IND values vides a reasonably good description. For perspectives on
between chemically different systems is not straightfor- valence bond theory, the reader is referred to e. g. [24, 25].
ward.
Looking for further insight, we re-expressed the many- weight of a12 e4 t21 AlV
1 2 2 2
body ground-state wave-functions in terms of atomic- weight of t2g t2g t2g t2g 4S
like, single-site orbitals. The orbital localization module 89% 8
e8

Ga d
4S

available in Orca was employed for this purpose; from

3
V4
5d
Ta

the 12 symmetry-adapted orbitals (1×a1 , 1×e, 1×t1 , 88%

S8
Ga

2×t2 ) obtained in the (7e,12o) CASSCF we arrive then 72% 48%

18%

GaV4Se8
to 12 t2g -like functions (three per pseudo-octahedrally 21% 89%
coordinated transition-metal ion, see Supplementary Fig- 15%
ure 1). For both orbital bases, symmetry-adapted or site-
centered, the weights of the leading configurations are
55%
illustrated in Fig. 3, for GaV4 S8 , GaV4 Se8 , GaNb4 S8 , 54%
GaNb4 Se8 , GaTa4 Se8 , and an A-site-substituted mem- 65% 67%
ber of the family (see also Supplementary Table 6). In- GaN
terestingly, a low weight of the a21 e4 t12 configuration in the b4 S 4d b 4S 8
symmetry-adapted orbital basis is associated with large
e8 GaN
weight of the t12g t22g t22g t22g (i. e., V4+ V3+ V3+ V3+ ) confi-
gurations in the localized-orbital representation; for the FIG. 3. Polar plot with weights for the leading con-
AlV4 S8 , GaV4 S8 , and GaV4 Se8 vanadates, in particular, figuration in symmetry-adapted (red) and localized
(blue) orbital basis. For each system, the analysis is per-
15-20% a21 e4 t12 translates into 85-90% configurations of
formed in terms of ground-state optimized CASSCF(7e,12o)
t12g t22g t22g t22g type. The remaining part stems mainly from wave-functions.
triply-occupied transition-metal centers, i. e., excited-
state configurations of t12g t22g t12g t32g (V4+ V3+ V4+ V2+ )
type. Weights of only ≈9% for the latter indicate
much stronger correlations in the case of V-based lacu-
nar spinels: intersite fluctuations are heavily suppressed, DISCUSSION
compared to the 4d and 5d compounds. In a Mott-
Hubbard picture, stronger localization is the result of To analyze in detail how correlations evolve from 3d to
larger U/t ratio. In other words, correlations are moder- 4d and 5d ions for the same type of leading ground-state
ate in the 4d and 5d compounds and strong in the vana- configuration and in the same crystallographic setting is
dates — for the latter, an expansion in terms of four difficult. 3d5 (Mn2+ , Fe3+ ) species, for example, tend to
V4+ V3+ V3+ V3+ resonant valence structures already pro- adopt a t32g e2g ground-state electron configuration, while
 4

4d5 (Ru3+ , Rh4+ ) and 5d5 (Ir4+ ) varieties display a t52g into the polar properties of these materials. An analysis
valence-orbital occupation. Thinking of lower d-shell fill- in terms of only three molecular-like t2 orbitals and one
ing, Mo5+ 4d1 and Os7+ 5d1 ions, for instance, can be electron as in e.g. Ref. [34] does not seem promising:
found in double-perovskite f cc settings [26], but that is according to our data, especially in the vanadates, the
not the case for Ti3+ or V4+ 3d1 . (a21 e4 )t12 description is not appropriate — the M4 tetra-
Here we individualize the group-5 lacunar spinels as a hedron t2 electron cannot be separated from the other
unique platform that makes it possible to illustrate how six d-ion valence electrons, symmetry breaking should be
correlations shape many-body wave-functions across a rather described in terms of resonating holes in localized
given group of the d block — 3d to 4d and 5d, for the same orbital basis (i.e. V4+ ‘holes’ in V3+ ‘background’).
kind of leading electron configuration and in the same In sum, our quantum chemical data provide unparal-
crystallographic setting. In particular, we provide new, leled specifics as concerns the correlated electronic struc-
important insights by expressing the many-body M4 - ture of the group-5 lacunar spinels, well beyond the fea-
tetrahedron wave-function in terms of localized single-ion tureless a21 e4 t12 picture circulated so far in the literature.
t2g orbitals. We show that in the vanadates strong corre- Stronger correlations in the vanadates imply substan-
lations yield a weight of 85–90% for the t12g t22g t22g t22g (i. e., tially less weight for the a21 e4 t12 configuration as compared
V4+ V3+ V3+ V3+ ) configurations; ferromagnetic double to the Nb and Ta compounds and render the molecular-
exchange shows up in this setting and yields near de- orbital picture [8, 9, 35] inappropriate. Remarkably, spin-
generacy of the low-lying low- and high-spin states — orbit coupling is still effective, even for the vanadates
the S = 1/2 doublet is obtained as single-tetrahedron — the predicted fine structure with a splitting of ≈10
ground-state term only through a more advanced many- meV between the j ≈ 3/2 and j ≈ 1/2 terms should be
body treatment. In contrast, smaller U/t ratios in the 4d detectable experimentally. The stronger intersite fluc-
(Nb) and 5d (Ta) systems take us away from the regime tuations (M 3+ M 3+ →M 2+ M 4+ ) and the larger weight
of strongly correlated electrons: in localized-orbital ba- (65-75%) of the a21 e4 t12 molecular-orbital configuration
sis, we see that stronger charge fluctuations reduce the in the Nb and Ta spinels indicate that the 4d and 5d
weight of t12g t22g t22g t22g resonances to ∼50%; in molecular- systems are closer to the Hartree-Fock limit. The differ-
orbital representation, significantly larger hoppings (t) ent nature of valence-space charge fluctuations across the
and consequently larger bonding-antibonding splittings group-5 family of lacunar spinels should be relevant to
make that the Aufbau principle is to first approximation inter-tetramer exchange; on-site charge fluctuations, for
usable, with weights in the range of 65-75% for the a21 e4 t12 example, were shown to strongly renormalize intersite ex-
configuration. change in cuprate superconductors [36]. Assessing coop-
This result suggests a physical picture for the non- erative effects in group-5 lacunar spinels through calcula-
magnetic states found in the Nb- and Ta-based lacunar tion of inter-cluster couplings will require approaches able
spinels: as the M4 -cluster electrons are prone to stronger to incorporate the correlated nature of the M4 -cluster
fluctuations with larger spatial spread, inter-cluster cou- ground states.
plings are able to create “valence bond” spin singlets, as
concluded from experiment [27–29]. The peculiar pseu-
dospin structure must play a role in the superconductiv- METHODS
ity mechanism under pressure, which is speculated to be
unconventional owing to closeness of magnetic states and The basic building block in the lacunar-spinel structure
spin fluctuations. was described by a [M 4 X 28 Ga6 ]25 – embedded cluster
While it is clear that the on-site correlations affect the model (M = V, Nb, Ta; X = S, Se) (see Fig. 1). Exper-
magnetic properties, they are only indirectly discernible imentally determined high-temperature lattice parame-
in available experimental data, as already pointed our ters were adopted, as reported by Stefancic et al. [22] for
for susceptibility [21, 22] and inelastic neutron scatter- GaV4 S8 and by Pocha et al. for GaNb4 Se8 and GaTa4 Se8
ing measurements [23] above. More direct experimental [7]. The influence of the surrounding bulk atoms was
insight into the details of the single-tetrahedron corre- modeled by a finite point charge field (PCF) generated
lated electronic structure might be derived from resonant through the Ewald program [37, 38]. A buffer region of
inelastic x-ray scattering experiments, as in the case of 60 capped effective core potentials (cECPs) was set up
other clustered compounds, either d- [30] or p-electron between the quantum cluster and PCF (indicated by the
[31–33] based. smaller atoms in Fig. 1) (for details, see Section I of the
Overall weights of ≳50% for the t12g t22g t22g t22g resonant Supplementary Information).
valence structures suggest the t-U -V model (or U -tt′ -V V ′ As initial step in our study, quasi-restricted or-
variants, where the primes denote inter-tetrahedral hop- bitals (QROs [39]) were generated from an unrestricted
ping matrix elements and Coulomb repulsion integrals) Kohn-Sham B3LYP calculation for a single-configuration
as means to explore correlation-induced symmetry break- S = 5/2 state with initial-guess orbitals from Hueckel
ing. Such numerical investigations could provide qualita- theory. The Hueckel guess ensures that the QROs ful-
tive insights into the different types of low-temperature fill Td point-group symmetry. Subsequently, 12 [M4 ]13+
lattice symmetries realized in lacunar spinels and also molecular orbitals around the HOMO-LUMO gap were
 5

identified from the QROs and used as a starting point [8] R. Pocha, D. Johrendt, and R. Pöttgen, Electronic and
for complete active space self-consistent field (CASSCF) Structural Instabilities in GaV4 S8 and GaMo4 S8 , Chem.
[17] calculations. Major convergence problems as encoun- Mater. 12, 2882 (2000).
tered in earlier quantum chemical studies [11] are circum- [9] H. Müller, W. Kockelmann, and D. Johrendt, The mag-
vented in this way. The valence-space multiplet structure netic structure and electronic ground states of mott in-
sulators GeV4 S8 and GaV4 S8 , Chem. Mater. 18, 2174
was derived from state averaged (SA) CASSCF optimiza-
(2006).
tions with those 12 orbitals and seven valence electrons [10] H.-S. Kim, J. Im, M. J. Han, and H. Jun, Spin-orbital en-
defining the active space (denoted in quantum chemistry tangled molecular jeff states in lacunar spinel compounds,
as (7e,12o) CASSCF), consequently corrected for dynam- Nat. Commun. 5, 3988 (2014).
ical correlation by N -electron valence 2nd order pertur- [11] L. Hozoi, M. S. Eldeeb, and U. K. Rößler, V4 tetrahedral
bation theory (NEVPT2) [18]. Both methods were accel- units in AV4 X8 lacunar spinels: Near degeneracy, charge
erated by the resolution of identity (RI [40]) and chain- fluctuations, and configurational mixing within a valence
of-spheres (COS [41]) approximations for Coulomb and space of up to 21 d orbitals, Phys. Rev. Res. 2, 022017(R)
exchange integrals with automatically generated auxil- (2020).
iary basis sets [42]. All calculations were done using the [12] T. Petersen, L. Prodan, V. Tsurkan, H.-A. Krug von
program package Orca, v5.0.3 [43]. Nidda, I. Kézsmárki, U. K. Rößler, and L. Hozoi, How
Correlations and Spin–Orbit Coupling Work within Ex-
tended Orbitals of Transition-Metal Tetrahedra of 4d/5d
Lacunar Spinels, J. Phys. Chem. Lett. 13, 1681 (2022).
Data Availability [13] T. Petersen, L. Prodan, K. Geirhos, H. Nakamura,
I. Kézsmárki, and L. Hozoi, Dressed jeff-1/2 objects in
mixed-valence lacunar spinel molybdates, Sci. Rep. 13,
The quantum chemical data (coordinates of quantum 2411 (2023).
clusters and point charge fields, Orca outputs, and mag- [14] H.-S. Kim, K. Haule, and D. Vanderbilt, Molecular Mott
netic susceptibility simulations) generated in this study state in the deficient spinel GaV4 S8 , Phys. Rev. B 102,
have been deposited in the RADAR database under the 081105(R) (2020).
DOI 10.22000/1655. [15] E. Ramos-Cordoba, P. Salvador, and E. Matito, Sep-
aration of dynamic and nondynamic correlation, Phys.
Chem. Chem. Phys. 18, 24015 (2016).
[16] R. Izsák, A. V. Ivanov, N. S. Blunt, N. Holzmann, and
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Competing Interests
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