text:
# Spin Order due to Orbital Fluctuations: Cubic Vanadates

## Abstract

We investigate the highly frustrated spin and orbital superexchange interactions in cubic vanadates. The fluctuations of $`t_{2g}`$ orbitals trigger a novel mechanism of ferromagnetic interactions between spins $`S=1`$ of V3+ ions along one of the cubic directions which operates already in the absence of Hund’s rule exchange $`J_H`$, and leads to the C-type antiferromagnetic phase in LaVO3. The Jahn-Teller effect can stabilize the orbital ordering and the G-type antiferromagnetic phase at low temperatures, but large entropy due to orbital fluctuations favors again the C-phase at higher temperatures, as observed in YVO3.

Large Coulomb interactions play a crucial role in transition metal oxides, and are responsible for the collective behavior of strongly correlated $`d`$ electrons which localize in Mott-Hubbard (or charge-transfer) insulators . Such localized electrons may occupy degenerate orbital states which makes it necessary to consider orbital degrees of freedom at equal footing with electron spins, and leads to the effective (superexchange) spin-orbital models to describe the low-energy physics . A remarkable feature of these models is that the superexchange interaction is highly frustrated on a cubic lattice, which was recognized as the origin of novel quantum effects in transition metal oxides . In case of $`e_g`$ orbital systems this frustration is likely removed by orbital order due to order-out-of-disorder mechanism, which maximizes the energy gain from quantum spin fluctuations . Moreover, quantum effects among $`e_g`$ orbitals are largely suppressed by the Jahn-Teller (JT) effect in real systems, which together with superexchange often leads to structural phase transitions accompanied by a certain ordering of occupied orbitals, supporting particular magnetic structures. Some well known examples are systems with degenerate $`e_g`$ orbitals filled either by one hole (KCuF3), or by one electron (LaMnO3), which order antiferromagnetically well below the structural transition.

The transition metal oxides with partly filled $`t_{2g}`$ orbitals exhibit different and more interesting phenomena. This occurs due to the relative weakness of the JT coupling in this case, and due to the higher degeneracy and additional symmetry of $`t_{2g}`$ orbitals . As a result, the orbitals may form the coherent orbital-liquid ground state stabilized by quantum effects, as observed in the spin $`S=1/2`$ Mott-insulator LaTiO3 . It is puzzling what happens when the $`t_{2g}`$ orbitals are filled by two electrons, as in vanadium oxides. On one hand, the occupied $`t_{2g}`$ orbitals are known to order in non-cubic vanadium compounds, such as LiVO2  and V2O3 . In fact, the first spin-orbital model for V2O3 with spins $`s=1/2`$ was proposed over twenty years ago , but later it was realized that $`J_H`$ at V$`{}_{}{}^{3+}(d^2)`$ ions is large , and the relevant model has to involve $`S=1`$ spins . On the other hand, the situation in cubic systems might be very different as all the bonds are a priori magnetically equivalent, and quantum fluctuations among orbitals are expected to play an important role in this case.

In this Letter we derive and investigate the spin-orbital model for cubic vanadates: LaVO3 and YVO3. The magnetic order in LaVO3 is C-type \[ferromagnetic chains along $`c`$-axis which stagger within $`(a,b)`$ planes\], with the Néel temperature $`T_N=140`$ K , while it is staggered in all three directions (G-type) in YVO3 at $`T<77`$ K and C-type at higher temperatures $`77<T<114`$ K . The C-phase is particularly surprising as arising from a practically undistorted structure of LaVO3 at $`T>T_N`$ . Recent Hartree-Fock studies have shown that indeed C- and G-phase are energetically close . In order to understand the microscopic origin of their competition we consider the regime of large $`U`$, and address below the following questions: (i) can the superexchange interactions alone explain why the ferromagnetic (FM) and antiferromagnetic (AF) interactions coexist in LaVO3 in spite of a practically ideal cubic structure at $`T>T_N`$ with almost equal V–V bonds; (ii) why the structural transition in LaVO3 occurs only below the magnetic transition; and (iii) why is the G-type AF order stable in the low-temperature phase of YVO3, while the C-type order wins at higher temperatures?

We start with a Mott-insulator picture of cubic vanadites, consistent with the large value of on-site intraorbital Coulomb element $`U4.5`$ eV , and with the results of electronic-structure calculations . Due to the Hund’s coupling $`J_H0.68`$ eV  the V3+ ions are in triplet configuration $`{}_{}{}^{3}T_{2}^{}`$. Each $`t_{2g}`$ orbital is orthogonal to one cubic axis. For instance, $`yz`$ is orthogonal to $`a`$ axis and will be labelled as $`a`$, while $`zx`$ and $`xy`$ will be labelled as $`b`$ and $`c`$, respectively. The electron densities at V3+ ions satisfy a local constraint, $`n_{ia}+n_{ib}+n_{ic}=2`$.

The superexchange interactions between $`S=1`$ spins arise from the virtual excitations $`d_i^2d_j^2d_i^3d_j^1`$ on a given bond $`ij`$, with the hopping $`t`$ allowed only between two out of three $`t_{2g}`$ orbitals. The $`d_i^3`$ excited state may be either a high-spin $`{}_{}{}^{4}A_{2}^{}`$ state, or one of three low-spin states: $`{}_{}{}^{2}E`$, $`{}_{}{}^{2}T_{1}^{}`$ or $`{}_{}{}^{2}T_{2}^{}`$ . When the second order processes $`d_i^2d_j^2d_i^3d_j^1d_i^2d_j^2`$ are analyzed, one has to project the $`d_i^3`$ ($`d_i^2`$) configuration generated after an individual hopping process on the above $`d_i^3`$ eigenstates ($`{}_{}{}^{3}T_{2}^{}`$ ground state). This leads to the spin-orbital Hamiltonian,

$$=J\underset{\gamma }{}\underset{ij\gamma }{}\left[(\stackrel{}{S}_i\stackrel{}{S}_j+1)\widehat{J}_{ij}^{(\gamma )}+\widehat{K}_{ij}^{(\gamma )}\right],$$
(1)
where the orbital operators $`\widehat{J}_{ij}^{(\gamma )}`$ and $`\widehat{K}_{ij}^{(\gamma )}`$ follow from the processes active on the bond $`ij\gamma `$, where $`\gamma =a,b,c`$:

$`\widehat{J}_{ij}^{(\gamma )}`$ $`=`$ $`{\displaystyle \frac{1}{2}}[(1+2\eta R)(\stackrel{}{\tau }_i\stackrel{}{\tau }_j+{\displaystyle \frac{1}{4}}n_in_j)`$ (2)
$``$ $`\eta r(\tau _i^z\tau _j^z+{\displaystyle \frac{1}{4}}n_in_j){\displaystyle \frac{1}{2}}\eta R(n_i+n_j)]^{(\gamma )},`$ (3)
$`\widehat{K}_{ij}^{(\gamma )}`$ $`=`$ $`[\eta R(\stackrel{}{\tau }_i\stackrel{}{\tau }_j+{\displaystyle \frac{1}{4}}n_in_j)+\eta r(\tau _i^z\tau _j^z+{\displaystyle \frac{1}{4}}n_in_j)`$ (4)
$``$ $`{\displaystyle \frac{1}{4}}(1+\eta R)(n_i+n_j)]^{(\gamma )},`$ (5)
and $`J=4t^2/U`$. The coefficients $`R=1/(13\eta )`$ and $`r=1/(1+2\eta )`$ originate from the multiplet structure of the $`t_{2g}^3`$ excited states via $`\eta =J_H/U`$ . The operators $`\stackrel{}{\tau }_i=\{\tau _i^x,\tau _i^y,\tau _i^z\}`$ are defined in the orbital pseudospin subspace spanned by two orbital flavours which are active along a given direction $`\gamma `$. For instance, for a bond $`ijc`$, the interactions follow from the electron hopping between the pairs of $`a`$ and $`b`$ orbitals, and may be expressed by Schwinger bosons: $`\tau _i^+=a_i^{}b_i`$, $`\tau _i^{}=b_i^{}a_i`$, $`\tau _i^z=\frac{1}{2}(n_{ia}n_{ib})`$, and $`n_i^{(c)}=n_{ia}+n_{ib}`$, and therefore:

$`2\left(\stackrel{}{\tau }_i\stackrel{}{\tau }_j+{\displaystyle \frac{1}{4}}n_in_j\right)^{(c)}`$ $`=`$ $`(n_{ia}n_{ja}+a_i^{}b_ib_j^{}a_j)+(ab),`$ (6)
$`2\left(\tau _i^z\tau _j^z+{\displaystyle \frac{1}{4}}n_in_j\right)^{(c)}`$ $`=`$ $`n_{ia}n_{ja}+n_{ib}n_{jb}.`$ (7)
Consider first the interactions in the $`J_H0`$ limit:

$$_0=\frac{1}{2}J\underset{\gamma }{}\underset{ij\gamma }{}(\stackrel{}{S}_i\stackrel{}{S}_j+1)\left(\stackrel{}{\tau }_i\stackrel{}{\tau }_j+\frac{1}{4}n_in_j\right)^{(\gamma )},$$
(8)
where a constant energy of $`2J`$ per V3+ ion is neglected. It is straighforward to understand why the interactions in this limit turn out to have the same structure as in LaTiO3 , where for $`s=1/2`$ spins of Ti3+ ions one finds instead $`(\stackrel{}{s}_i\stackrel{}{s}_j+\frac{1}{4})`$. In fact, the spin interactions follow entirely from the Pauli principle, as the terms $`\stackrel{}{S}_i\stackrel{}{S}_j`$ due to the high-spin $`{}_{}{}^{4}A_{2}^{}`$ and low-spin $`{}_{}{}^{2}E`$ states, which involve $`d^3\{abc\}`$ configurations, cancel each other.

A remarkable feature of the $`t_{2g}`$ superexchange in Eq. (8) is that every bond is represented by two equivalent orbitals giving a SU(2) symmetric structure $`(\stackrel{}{\tau }_i\stackrel{}{\tau }_j+\frac{1}{4}n_in_j)^{(\gamma )}`$ of the orbital part. Depending on the type of orbital correlations this may result in a spin coupling constant of either sign. This important property resembles that of one-dimensional (1D) SU(4) model . The present problem is however more involved since there are three $`t_{2g}`$ flavours in a cubic crystal, and SU(2) orbital correlations among two of them along a particular direction will necessarily frustrate those correlations in other directions. One may also notice a certain analogy with the models of valence bond solids : Actually, a large orbital moment $`L=1`$ of $`t_{2g}`$ states is formally decomposed in Eq. (8) onto pseudospins one-half, active on different bonds. The analogy is again only partial since independent rotations within orbital doublets active on different bonds are not allowed here by construction, and thus the formation of orbital singlets in all directions simultaneously is impossible.

Another key observation is the difference between the interactions derived for the pairs of Ti3+ and V3+ ions: In the $`d^1`$ configuration spin $`s=1/2`$ is small, and the idea of composite spin-orbital resonance, in analogy to SU(4) excitations , helped to resolve the orbital frustration problem . In that case the superexchange is best optimized by the spin-orbital resonance in all three directions, and the orbitals form a three-dimensional quantum liquid which coexists with weak spin order of G-type. This mechanism is however suppressed in the present case of large spin $`S=1`$ at $`d^2`$ ions, and the quantum energy can be gained mainly from the orbital sector. This suggests that a particular classical spin configuration may be picked up which maximizes the energy gain from orbital fluctuations. Indeed, orbital singlets (with $`n_{ia}+n_{ib}=1`$) may form on the bonds parallel to $`c`$ axis, exploiting fully the SU(2) symmetry of the orbital interactions in one direction, while the second electron occupies the third $`t_{2g}`$ orbital ($`n_{ic}=1`$), controlling spin interactions in the $`(a,b)`$ planes.

In order to understand why orbital fluctuations support the C-AF type spin order, it is instructive to start with a single bond along $`c`$-axis. A crucial observation is that the lowest energy of $`J/2`$ is obtained when the spins are ferromagnetic, and the orbitals $`a`$ and $`b`$ form a singlet, with $`\stackrel{}{\tau }_i\stackrel{}{\tau }_j^{(c)}=\frac{3}{4}`$ . Thus, one finds a novel mechanism of ferromagnetic interactions which operates due to local fluctuations of $`a`$ and $`b`$ orbitals. At the same time, the orbital resonance on the bonds in $`(a,b)`$ planes is blocked, as $`n_{ic}=n_{jc}=1`$, and the superexchange is AF due to the excitations to $`{}_{}{}^{2}T_{1}^{}`$ and $`{}_{}{}^{2}T_{2}^{}`$ states with doubly occupied $`c`$ orbitals. Such an electron distribution and the formation of quasi-1D orbital pseudospin chains supports FM spin order along $`c`$ axis in C-phase, and could be stable only at low temperature when a coherent spin state breaking the cubic symmetry is formed as well. The onset of the magnetic order which coexists with such orbital fluctuations explains also why a structural transition is here induced by this coherent electronic state.

We compared the ground state energies of C- and G-phase using the spin-wave theory for the spin part, while either the exact Bethe ansatz result, or the Gaussian fluctuations around the ordered state, were used for the orbital part. The exchange constants within $`(a,b)`$ planes ($`J_{ab}>0`$) and along $`c`$ axis ($`J_c<0`$) determine the spin waves. They follow from Eqs. (1)–(4) (in units of $`J`$):

$`J_c`$ $`=`$ $`{\displaystyle \frac{1}{2}}\left[(1+2\eta R)\stackrel{}{\tau }_i\stackrel{}{\tau }_j+{\displaystyle \frac{1}{4}}^{(c)}\eta r\tau _i^z\tau _j^z+{\displaystyle \frac{1}{4}}^{(c)}\eta R\right],`$ (9)
$`J_{ab}`$ $`=`$ $`{\displaystyle \frac{1}{4}}\left[1\eta (R+r)+(1+2\eta R\eta r)n_{ia}n_{ja}^{(b)}\right],`$ (10)
and are given by orbital correlations. Their values at $`\eta =0`$ are easily obtained from the Bethe ansatz result for a 1D Heisenberg chain of disordered $`a`$ and $`b`$ orbitals (in this case $`n_{ia}n_{ja}^{(b)}=\frac{1}{4}`$): $`J_{ab}=0.313`$ and $`J_c=0.097`$. Although the FM interaction along $`c`$-axis $`J_c`$ is weaker in this limit, it gives a considerable energy gain of $`0.2J`$ over the G-AF order. It is further enhanced at $`J_H>0`$ by a mechanism similar to that known from cuprates and manganites , as the high-spin $`{}_{}{}^{4}A_{2}^{}`$ state lies by $`3J_H2.0`$ eV below its low-spin $`{}_{}{}^{2}E`$ counterpart. This splitting modifies the 1D orbital-wave (OW) spectrum,

$$\omega _k^\mathrm{C}=\sqrt{\mathrm{\Delta }^2+R^2(1\mathrm{cos}^2k)},$$
(11)
and the gap $`\mathrm{\Delta }=\{\eta (R+r)[2R+\eta (R+r)]\}^{1/2}`$ opens. Using the spin-wave theory we determined the orbital correlations in Eqs. (9). As a result, one finds increasing (decreasing) FM (AF) exchange constants with increasing $`J_H`$ (Fig. 1). Taking a representative value of the hopping integral $`t=0.2`$ eV gives $`J=35.6`$ meV which leads to the exchange constants in the C-phase obtained for a realistic ratio $`J_H/U=0.15`$: $`J_{ab}7.1`$ and $`J_c9.3`$ meV. These values are in the expected range, taking the Néel temperature $`T_N=140`$ K of the C-phase in LaVO3. We emphasize that the orbital quantum fluctuations play here a dominating role and the well known Hund’s mechanism due to $`J_H`$ alone would not suffice to obtain $`|J_c|>J_{ab}`$, giving instead $`J_c4.4`$ meV.

Next we consider the reasons for the stability of the G-phase in YVO3. Unlike LaVO3 with almost equal V–V bonds , this compound crystalizes in the distorted structure , indicating that the JT effect plays a significant role. It was suggested that energy may be gained due to C-type orbital ordering, with $`a`$ and $`b`$ orbitals staggered in $`(a,b)`$ planes and repeated along c-axis, while $`n_{ic}=1`$ . Such ordering can be promoted by

$$H_{\mathrm{JT}}=2V\underset{ijc}{}\tau _i^z\tau _j^z+V\underset{ij(a,b)}{}\tau _i^z\tau _j^z,$$
(12)
and competes with the orbital disorder. This behavior is remarkably different from the $`e_g`$ systems, where the JT effect and superexchange support each other, inducing orbital ordering . While $`V>0`$ causes orbital splitting by $`4V`$ and thus lowers the energy of the G-phase ($`E_\mathrm{G}`$), it has little effect on the energy of the C-phase ($`E_\mathrm{C}`$). The energy difference is given by

$$\mathrm{\Delta }E=E_\mathrm{C}E_\mathrm{G}V\frac{1}{2}\eta (3R+r)\delta E_{\mathrm{OW}},$$
(13)
where $`\delta E_{\mathrm{OW}}>0`$ is the energy contribution due to quantum fluctuations of $`t_{2g}`$ orbitals. Large spins $`S=1`$ are almost classical and their fluctuations could be neglected.

Orbital excitations are quite different in both AF phases: while the gap $`\mathrm{\Delta }`$ is small and grows $`\sqrt{\eta }`$ in C-phase (11), a large gap $`4V`$ opens in the OW spectrum of G-phase, $`\omega _k^\mathrm{G}=4V+\eta R\mathrm{cos}k`$. Thus, both the larger quantum fluctuations and additional (classical) energy gain due to finite $`J_H`$ in the C-phase have to be overbalanced by the JT energy $`V`$ in order to stabilize the G-AF order at $`T0`$. However, the G-phase may be destabilized at finite $`T`$ by larger orbital entropy of the C-phase. Indeed, taking $`V=0.65J`$ and $`\eta =0.15`$, the free energy, $`=T𝒮`$, with the entropy $`𝒮`$ determined by orbital excitations, gives a transition from G- to C-phase around $`T^{}0.8J`$ (Fig. 2). While this behavior reproduces qualitatively the first order transition observed in YVO3 , its quantitative description requires a careful consideration of lattice and spin entropy contributions to the free energy $``$. These effects are expected to reduce the transition temperature $`T^{}`$ down to experimental values.

The exchange constants in the G-phase are anisotropic which can be understood by analyzing the superexchange expressions (9). The transitions to the low-spin $`{}_{}{}^{2}T_{1}^{}`$ and $`{}_{}{}^{2}T_{2}^{}`$ states occur in all three directions between pairs of occupied orbitals of the same kind, and give the leading AF contribution $`(1\eta r)`$. The excitations of $`d^3\{abc\}`$ configurations occur in addition on the bonds in the $`(a,b)`$ planes, and reduce the AF coupling $`J_{ab}`$ by $`\eta R`$, giving $`J_{ab}<J_c`$. Including in addition a relativistic spin-orbit coupling $`\mathrm{\Lambda }`$ ($`18`$ meV ), we find for the G-phase:

$`J_c`$ $`=`$ $`{\displaystyle \frac{1}{4}}(1\eta r){\displaystyle \frac{1}{2}}(1+2\eta R\eta r)\overline{\mathrm{\Lambda }}^2,`$ (14)
$`J_{ab}`$ $`=`$ $`{\displaystyle \frac{1}{4}}(1\eta R\eta r)+{\displaystyle \frac{1}{4}}(1+2\eta R\eta r)\overline{\mathrm{\Lambda }}^2,`$ (15)
where $`\overline{\mathrm{\Lambda }}=\mathrm{\Lambda }/4V`$. The spin-orbit coupling enhances (reduces) the effective superexchange in $`(a,b)`$ planes (along $`c`$-axis), as shown in Fig. 3. For example, taking a value of $`\mathrm{\Lambda }/4V=0.2`$ which is believed to be close to realistic for YVO3 , we find $`J_{ab}5.9`$ and $`J_c6.9`$ meV. These values lie in the expected range for the G-phase of YVO3. This also demonstrates that the magnetic structure and the spin-wave spectrum are completely different depending on the orbital state — the exchange constant $`J_c`$ which is FM in LaVO3 may become even the strongest AF bond when the orbitals have ordered, as in YVO3, and the JT splitting (12) dominates over the spin-orbit coupling.

Summarizing, strong $`t_{2g}`$ orbital fluctuations in a half-filled system of $`yz`$ and $`zx`$ orbitals in cubic vanadites lead to a new mechanism of ferromagnetic superexchange which stabilizes the C-phase in first undistorted LaVO3, and the structural transition follows. The JT effect opposes the superexchange and can stabilize the G-phase with orbital ordering but only at low temperatures, as the fluctuations of $`t_{2g}`$ orbitals release high entropy, and are thus responsible for the transition from the orbital ordered G-phase to the orbital disordered C-phase, observed in YVO3.

We thank B. Keimer, Y. Tokura and L. F. Feiner for stimulating discussions. A.M.O. acknowledges the support by the Committee of Scientific Research (KBN) of Poland, Project No. 2 P03B 055 20.