# The electronic structure of the heavy fermion metal LiV2O4

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## Abstract

The electronic structure of the first reported heavy fermion compound without f-electrons LiV<sub>2</sub>O<sub>4</sub> was studied by an ab-initio calculation method. In the result of the trigonal splitting and d-d Coulomb interaction one electron of the $`d^{1.5}`$ configuration of V ion is localized and the rest partially fills a relatively broad conduction band. The effective Anderson impurity model was solved by Non-Crossing-Approximation method, leading to an estimation for the single-site Kondo energy scale $`T_K`$. Then, we show how the so-called exhaustion phenomenon of Nozières for the Kondo lattice leads to a remarkable decrease of the heavy-fermion (or coherence) energy scale $`T_{coh}T_{K}^{}{}_{}{}^{2}/D`$ ($`D`$ is the typical bandwidth), comparable to the experimental result.

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Heavy fermion systems are characterized by a large effective quasiparticle mass inferred from the strongly enhanced electronic specific heat coefficient and spin susceptibility at low temperatures . Until recently this effect was observed only for f-electron compounds containing lanthanide or actinide atoms. The transition metal oxide compound LiV<sub>2</sub>O<sub>4</sub> is the first reported heavy fermion system without f-electrons .

LiV<sub>2</sub>O<sub>4</sub> has a face-centered-cubic normal-spinel structure. The formal valence of the V-ions is $`V^{3.5+}`$ leading to 1.5 electrons/V in the 3d-band. The electronic specific heat coefficient $`\gamma (T)=C_e(T)/T`$ is extraordinarily large for a transition metal compound $`(\gamma (1K)0.42J/molK^2)`$, decreasing rapidly with the temperature to $`0.1J/molK^2`$ at 30 K. The spin susceptibility from 50K to 400K shows a Curie-Weiss \[$`\chi =C/(T\theta )`$\] behavior corresponding to weakly antiferromagnetically coupled ($`\theta `$= -30 to -60 K) vanadium local magnetic moments with $`S`$=1/2 and $`g2`$, but static magnetic ordering does not occur above 0.02 K and superconductivity is not observed above 0.01 K. The nearly temperature independent spin susceptibility $`\chi (T)`$ and Knight shift $`K(T)`$ for $`T<30K`$ are a sign of the disappearance of the V local moment in this temperature region .

In the traditional heavy fermion compounds there are two distinct types of electronic states, the localized f-orbitals of lanthanide or actinide atoms which form local moments and the delocalized s-, p-, d-orbitals which are responsible for the metallic properties. The weak hybridization of the f-orbitals with the conduction states leads to the low temperature anomalies. If one of the 1.5 3d-electrons per V ion would be in a localized orbital, and the rest in a relatively broad band, then the situation would be analogous to f-compounds and all experimental facts could be qualitatively understood . As the general opinion was that these 1.5 electrons are in the (same) band formed by $`t_{2g}`$-orbitals, such a model was considered to be unrealistic. In this paper we will show that the trigonal point group symmetry of the V ion in LiV<sub>2</sub>O<sub>4</sub> lifts the degeneracy of the $`t_{2g}`$-band. As a result the above mentioned model, is appropriate to estimate the heavy-fermion energy scale for this compound.

The normal-spinel crystal structure is formed by the edge-shared oxygen octahedra with V-atoms at the centres and Li-atoms between octahedra. The face-centered-cubic lattice has four V atoms in the unit cell which form a tetrahedron (Fig. 1). The total space group of the crystal is cubic but the local point group symmetry of V-ion crystallographic position is trigonal. The different trigonal axes of every V-atom in the unit cell are directed towards the centre of the tetrahedron.

The octahedral coordination of the oxygen ions around the V results in the strong splitting of d-states into triply degenerate $`t_{2g}`$-orbitals with lower energy and double degenerate $`e_g`$-orbitals with higher energy. The band structure has three well separated sets of bands, completely filled O-2p-band, partially filled $`t_{2g}`$ band and empty $`e_g`$ bands. As only partially filled bands are important for the physical properties we will restrict our analysis to the $`t_{2g}`$ band.

In the trigonal symmetry crystal field the three $`t_{2g}`$ orbitals are split into the nondegenerate $`A_{1g}`$ and double degenerate $`E_g`$ representations of the $`D_{3d}`$ group. The $`A_{1g}`$-orbital is $`(xy+xz+yz)/\sqrt{3}`$ if the the coordinate axes are directed along V-O bonds. If the $`z`$-direction is chosen along the trigonal axis then the $`A_{1g}`$-orbital is $`3z^2r^2`$ (see Fig. 1) and the $`E_g`$ orbitals have the lobes in the plane perpendicular to $`z`$.

We have performed LDA calculations of the electronic structure of LiV<sub>2</sub>O<sub>4</sub> by LMTO method . In Fig. 2 the results for $`t_{2g}`$ band are presented with the partial DOS projected to $`A_{1g}`$ and $`E_g`$ orbitals. While the partial $`E_g`$ DOS have the width of $``$ 2 eV, the $`A_{1g}`$ DOS is much narrower (a width of only $``$ 1 eV). The trigonal splitting is smaller than the band width but it is not neglegible. We have estimated it as a difference of the centres of gravities of $`A_{1g}`$ and $`E_g`$ DOS’s and have found that the energy of $`A_{1g}`$ orbital is 0.1 eV lower than the energy of $`E_g`$ orbitals.

We have calculated the d-d Coulomb interaction parameter $`U`$  and have found the value of 3 eV, which is larger than the band width $`W`$ 2 eV. Such value of the $`U/W`$ ratio leads to the appearance of lower and upper Hubbard bands with one electron localized in the former and the other 0.5 partially filling the latter. Which particular orbital will form the lower Hubbard band is defined by the sign of the trigonal splitting between the energies of $`A_{1g}`$ and $`E_g`$ orbitals.

The effect of the d-d Coulomb interaction on the electronic structure of transition metal compounds can be treated by LDA+U method . This method is basically a combination of the Hartree-Fock approximation to multiband Hubbard model with LDA. The ground state of the LDA+U solution was found to be indeed a metal with one electron nearly completely localized on $`A_{1g}`$ orbital and $`E_g`$ orbitals forming relatively broad ($``$ 2 eV) band which is partially filled.

The partial DOS for $`E_g`$ orbitals has a long low-energy tail (Fig. 2) and as a consequence the LDA-occupancy of $`E_g`$ orbital is significantly larger than the corresponding value for $`A_{1g}`$ orbital. One would expect that after switching on the Coulomb interaction in LDA+U calculation, the orbital whose occupation was larger becomes in the process of the self-consistency iteration, more and more occupied at the expense of all other orbitals and in the end the d-electron will be localized on one of the $`E_g`$ orbitals. In reality the situation is more complicated. Indeed, the Coulomb interaction energy will be lowered by localization of the electron on any orbital. However the total energy of the solution with the localized electron on $`A_{1g}`$ orbital is lower than energy of the solution with $`E_g`$ orbital due to the trigonal splitting. The rotation invariant formulation of the LDA+U method allows the system to choose itself on what particular orbital (or the particular combination of the basis set orbitals) electrons will be localized. If one starts from the LDA orbital occupancies, than at the first stage of the self-consistency iterations the $`E_g`$ orbital, having larger LDA occupation become localized. However further iterations cause ‘rotations’ in the five-dimensional space of 3d-orbitals leading to the solution with the $`A_{1g}`$ orbital occupied. The system arrives at this solution independently of the starting point. The total energy as a functional of the orbital occupation matrix has only one minimum and the corresponding LDA+U equations have only one solution. The separation of the $`t_{2g}`$-states into the localized $`A_{1g}`$ orbital and the conduction band $`E_g`$ orbitals shows that LiV<sub>2</sub>O<sub>4</sub> can be regarded as an analog of f-systems. In order to estimate the strength of the interaction between the localized and the conduction electrons we have defined an effective Anderson impurity model. The partial DOS for $`A_{1g}`$ orbital obtained in the LDA+U calculation $`n_{A_{1g}}(E)`$ was used to determine the position of the impurity state $`ϵ_f`$ and the hybridization function $`\mathrm{\Delta }(E)`$:

$$n_{A_{1g}}(E)=\frac{1}{\pi }\mathrm{}m(Eϵ_f+i\mathrm{\Delta }(E))^1$$
(1)   
The results are presented on Fig. 3. We then used the LDA+U results as input to estimate the Kondo energy scale for a single site model. To solve this Anderson impurity model we have used a resolvent perturbation theory.

Within this approach one determines the renormalization of the impurity states by the hybridization with the surrounding medium. The latter is given by the hybridization function $`\mathrm{\Delta }(E)`$. The approach leads to a perturbation expansion in terms of $`\mathrm{\Delta }(E)`$. A widely used approximation, the Non-Crossing-Approximation (NCA) , is well-known to reproduce the low-energy scale of the underlying model , which is the single-site Kondo temperature $`T_K`$. Here we have extracted this quantity directly from the singlet-triplet splitting of the impurity states. For the hybridization function $`\mathrm{\Delta }(E)`$ shown in Fig. 3 we estimate for the single-site Kondo temperature $`T_K`$ 550K. On the other hand the Kondo temperature can be expressed via a Kondo parameter $`J_K`$ as :

$$T_K=De^{\frac{1}{2N(0)J_K}}$$
(2)   
where $`D`$ is the effective Fermi energy and $`N(0)`$ the density of conduction states per spin. In ref. the value of $`N(0)`$ was estimated from the experimental value of the Pauli susceptibility as 2.9 state/(eV vanadium spin direction). With a $`D`$ value of approximately 1 eV, this gives us an estimation for $`J_K`$ 670K. In contrast to standard f-systems where the direct exchange between localized f-electrons and conduction electrons is small, both localized and conduction electrons are 3d-electrons in our case and there is a strong onsite exchange coupling between them, namely a ferromagnetic Hund coupling of the order of 1eV. The presence of two types of d-electrons, namely those in conduction states and the electrons forming local moments, is known to result in a lattice in a double exchange ferromagnetic interaction between local moments. We have estimated this value of the intersite exchange coupling parameter from the results of LDA+U calculation using the formula derived as a second derivative of the total energy in respect to the angle between local moments directions . Our calculation gave the value of the double exchange parameter $`J_{dex}`$= 530K.

However, there is another contribution to the interaction between the local moments. The Kondo exchange is between a local moment (electron on the $`A_{1g}`$-orbital) on one site and the spin of the conduction electron ($`E_g`$ -orbital) on the neighboring site, because having different symmetry the orbitals do not mix on the same site. As the spins of the $`E_g`$ and $`A_{1g}`$ electrons on the neighboring site are ‘strongly’ coupled by the Hund interaction, it gives us an effective antiferromagnetic (AF) interaction between local moments on neighboring sites approximately equal to the Kondo exchange parameter $`J_K`$. As a result there is a strong cancellation between these two processes, ferromagnetic double exchange and AF Kondo-induced exchange so that the net exchange interaction is small. Simply substracting the two terms leads to an estimate $`J_K`$-$`J_{dex}140K`$. The measured Curie-Weiss $`\mathrm{\Theta }`$ at high temperature $`(\mathrm{\Theta }50K)`$ points to a more complete cancellation and a net AF exchange interaction that is an order in magnitude smaller than our estimate. This discrepancy is not surprising in view of the difficulty of making a reliable estimate in the presence of this strong cancellation. Note the inherent frustration that inhibits the onset of AF-order in a spinel lattice does not enter the determination of the value of $`\mathrm{\Theta }`$. The small value of $`\mathrm{\Theta }`$ shows that the net exchange interaction between neighboring local moments is very weak.

A realistic lattice model for LiV<sub>2</sub>O<sub>4</sub> contains two competing terms which couple the conduction and localized states. These are the onsite Hund’s ferromagnetic coupling and the AF Kondo interaction which couples conduction and localized electrons on neighboring sites. This competition makes difficulties for a first principles treatment. On the other hand, there are several arguments in favor of ignoring the ferromagnetic interactions relative to the Kondo interaction. For a single localized site, it is well-known that the onsite ferromagnetic coupling between conduction and localized states scales to weak coupling limit at low temperatures and so can be ignored. However it could be argued that in the lattice this ferromagnetic coupling scales to the strong coupling limit through the well-known double exchange effect. But as discussed above the double exchange effect is cancelled here by the AF interaction between the localized spins induced by the Kondo effect. Therefore it seems plausible to ignore at least as a first step the ferromagnetic interactions and treat only the AF interaction so that the model is simply a Kondo lattice model. There may be some renormalization of the Kondo exchange parameter, $`J_K`$ but for now we ignore that too.

In the Kondo lattice model there is also a competition between the induced AF interactions which favor AF order and the Kondo effect which favors a singlet groundstate. Here, the former are very weak due to the cancellation affects discussed above and as a result we are in the limit where the Kondo effect dominates. This leads to the formation of a heavy-fermion Landau Fermi liquid with a characteristic temperature scale for the onset of quantum coherence, $`T_{coh}`$. The exact value of $`T_{coh}`$ is difficult to estimate but there are a number of strong arguments that $`T_{coh}T_K`$, the single site Kondo temperature. We summarize these arguments below.

In the single site case, the local moment forms a singlet pair with any conduction electron within an energy $`T_K`$ of the Fermi energy. We have the picture of a complex screening cloud which delocalizes the impurity at the Fermi level. The resulting non-perturbative ground state is found to be of Fermi-liquid type, where all the physical quantities depend on $`T_K`$. In the concentrated Kondo lattice, the number of conduction electrons per site to screen the local moments is of order $`\text{n}_k=\frac{T_K}{D}1`$. There is a lack of conduction electrons to screen all the spin array at the energy scale $`T_K`$: this is the well-known exhaustion phenomenon. In that sense, a macroscopic singlet ground state should not take place at $`T_K`$, but rather at a very low temperature $`T_{coh}`$. To obtain it, we can use the following simple thermodynamical arguments. The condensation energy that we really dispose to screen the (effective) localized spins is: $`\text{E}_{cond}=\text{N}_V\text{n}_kT_K`$ where $`\text{N}_V`$ is the total number of V-ions (we have one localized 3d-electron per V). In view to stabilize a perfect singlet ground state, this energy must absorb all the entropy of the impurity lattice which is defined as: $`\text{S}_{tot}=\text{N}_V\mathrm{ln}2`$. Then, the energy scale at which the entropy of the spin array will go to zero can be simply defined as $`T_{coh}=\text{E}_{cond}/\text{S}_{tot}\text{n}_kT_K=T_{K}^{}{}_{}{}^{2}/D`$. For $`TT_{coh}`$, the prevalent bonds should be formed between local moments and then $`T_{coh}`$ plays the role of the effective Kondo temperature in the lattice problem. It should be noted that these effects predicted by physical arguments could recently be indeed observed in calculations for the periodic Anderson model in the framework of the Dynamical Mean-Field Theory . Taking into account the estimations for $`T_K`$ and $`D`$, we obtain $`T_{coh}2540K`$, which agrees well with the numerical result for the periodic Anderson model. It also seems to be in good agreement with the experimental result in LiV<sub>2</sub>O<sub>4</sub>. This should produce an enhanced linear specific heat and Pauli susceptibility which are proportional to $`N_V/T_{coh}`$, and a (normalized) Wilson ratio $`R_W`$ which is equal to one. Experimentally, $`R_W`$ is on the order of unity as in conventional heavy-metals.

In conclusion, our calculations using the LDA+U method give a theoretical justification of a model with one of the 3d-electrons per V localized in a $`A_{1g}`$-orbital and the remaining 0.5 electron/V in a conduction band state, primarily of $`E_g`$ symmetry, which has been previously discussed. This leads to a lattice model with competing onsite ferromagnetic coupling due to the Hund’s rule and nearest neighbor antiferromagnetic coupling due to the Kondo effect. We present arguments that such a model reduces to a Kondo lattice model. Estimates for the temperature scale for the onset of quantum coherence give a small value, much less than the single site Kondo temperature, in agreement with experiments. The low temperature heavy fermion Fermi liquid is strongly correlated and is therefore a good candidate for a transition to unconventional superconductivity, if it can be made perfect enough.

Note added—Recently an LDA calculation of the electronic structure of LiV<sub>2</sub>O<sub>4</sub> was made by Eyert et al. where the partial density of states of $`t_{2g}`$ band was analyzed using trigonal symmetry but the possibility of orbital polarization of electrons due to the Coulomb interaction was not investigated.

We wish to thank D. Johnston, D. Khomskii and D. Cox for stimulating discussions. This work was supported by the Russian Foundation for Basic Research (grants RFFI-98-02-17275 and RFFI-96-15-96598).