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# Discussion of a spin-cluster model for the low temperature phase of 𝛼’-NaV2O5

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## Abstract

We discuss magnetic excitations of a spin-cluster model which has been suggested to describe the low temperature phase of $`\alpha `$’-NaV2O5. This model fulfills all symmetry criteria proposed by recent x-ray investigations. We find that this model is not able to describe the occurence of two well separated magnon lines perpendicular to the ladder direction as observed in INS experiments. We suggest further experimental analysis to generally distinguish between models with double reflection or inversion symmetry.

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The modeling of the low temperature phase of NaV2O5 has initiated a discussion of effective spin models for the low-lying magnetic excitations. NaV2O5 undergoes a phase transition at Tc = 34K  associated with a lattice distortion, charge ordering and the opening of a spin gap. In NaV2O5 the V-ions are arranged in staggered ladders along the crystallographic $`b`$-axis. While in the high temperatur phase there is only one V4.5+ site, recent x-ray diffraction studies  suggest that in the low temperature phase there are three distinct valence states: on every other ladder one finds a zig-zag charge ordering of V4+ and V5+ valence states while on the intermediate ladders one finds rungs with two V4.5+ sites. The structural investigation further indicates that the space group of the low temperature phase is $`Fmm2`$. In the $`a`$-$`b`$ plane one finds a doubling of the unit cell along a and b as well as mirror planes $``$a and $``$b. The latter criterion generally excludes models with dimerization along in-line or zig-zag chains .

Recent inelastic neutron scattering experiments  show that there are two close-by magnon excitations with a gap of 8.75 meV and 10.65 meV. Both excitations have a large dispersion along the $`b`$-axis. The magnetic exchange coupling along b has been estimated to range between 37.9 meV  and 60 meV . The dispersion along a shows only a weak modulation of about 0.5 meV which is out of phase for the two well seperated branches. Raman scattering experiments  observe three excitations below the two magnon continuum which have been interpreted as singlet excitations. Remarkably, the lowest excitation has a gap that seems to coincide with the gap of the lower branch of the two magnon excitations.

Based on recent x-ray diffraction experiments in the low temperature phase de Boer et al.  proposed the formation of weakly coupled, frustrated spin-clusters along the crystallographic $`b`$-axis . Each cluster (see Fig. 1) contains six Vanadium atoms distributed over three ladders and and an overall number of four unpaired electrons which form a singlet ground state. This spin-cluster model is the only proposed model that obeys double reflection symmetry.

A previous theoretical study  addressed the applicability of the one-dimensional arrangement to model the strong magnon dispersion along the crystallographic $`b`$-axis. Using a novel cluster-operator theory as well as exact diagonalization and DMRG calculations the authors concluded that there is no parameter regime which would reproduce the observed $`b`$-axis dispersion.

In this paper, we present a study of the proposed spin-cluster model by means of a strong-coupling expansion. We calculate high order results for the magnon dispersions along the $`b`$-axis as well as the leading contribution along the $`a`$-axis. We discuss several mechanisms to explain the occurence of two low l ying magnon branches without finding a profound supporting argument. We point out that symmetries of the magnon dispersions can be used to distinguish between classes of models with reflection and inversion symmetry. Further, we study the occurence of singlet states in the spin-cluster model in terms of the reported Raman observations. We find that there is no evidence for a low lying singlet excitation of comparable energy to the lowest triplet excitation.

The Hamiltonian of the spin-cluster model reads

$`H`$ $`=`$ $`J_1{\displaystyle \underset{n}{}}𝐒_{1,n}𝐒_{2,n}+J_2{\displaystyle \underset{n}{}}𝐒_{1,n}𝐒_{2,n+1}`$ (4)
$`+J^{}{\displaystyle \underset{n}{}}(𝐒_{1,n}+𝐒_{2,n})(𝐒_{3,n}+𝐒_{4,n})`$
$`+J_3{\displaystyle \underset{n}{}}(𝐒_{2,n}𝐒_{}^{}{}_{3,n}{}^{}+𝐒_{4,n}𝐒_{}^{}{}_{1,n}{}^{}`$
$`+𝐒_{4,n}𝐒_{}^{}{}_{2,n+1}{}^{}+𝐒_{1,n}𝐒_{}^{}{}_{3,n+1}{}^{}),`$
where the $`𝐒_{i,n}`$ and $`𝐒_{}^{}{}_{i,n}{}^{}`$ denote the four spins on the $`n`$’th cluster of two neighboring b-axis chains. $`J_1=(1+\delta )J`$ and $`J_2=(1\delta )J`$ are alternating interactions along the $`b`$-axis and $`J_3`$ is the interaction along the $`a`$-axis. All interactions $`J`$, $`J^{}`$ and $`J_3`$ are assumed to be antiferromagnetic.

For an isolated cluster, $`J_2=J_3=0`$, we have two singlet, three triplet and one quintuplet eigenstates. We denote the low-lying eigenstates as follows:

$`\psi _1`$ $`=`$ $`{\displaystyle \frac{1}{\sqrt{3}}}\left[t_{12}^+t_{34}^{}+t_{12}^{}t_{34}^+t_{12}^0t_{34}^0\right],`$ (5)
$`\psi _2`$ $`=`$ $`s_{12}^{}s_{34}^{},\psi _3^\alpha =s_{12}^{}t_{34}^\alpha ,`$ (6)
$`\psi _4^0`$ $`=`$ $`{\displaystyle \frac{1}{\sqrt{2}}}\left[t_{12}^{}t_{34}^+t_{12}^+t_{34}^{}\right],`$ (7)
where $`s_{ij}`$ and $`t_{ij}^\alpha `$ are singlet and triplet states of the spins at sites $`i`$ and $`j`$ and $`\psi _4^0`$ is the $`S^z=0`$ component of the triplet $`\psi _4^\alpha `$. The corresponding energies are $`E_1=2J^{}+\frac{1}{4}J_1`$, $`E_2=E_3=\frac{3}{4}J_1`$ and $`E_4=J^{}+\frac{1}{4}J_1`$.

The ground state of the spin-cluster is the singlet state $`\psi _1`$ for antiferromagnetic couplings $`J`$ and $`J^{}`$ with $`J^{}>\frac{1}{2}J_1`$. For smaller values of $`J^{}`$ the ground state lies in the four-fold degenerate manifold of the states $`\psi _2`$ and $`\psi _3^\alpha `$. In first order, the inter-cluster coupling $`J_2`$ lowers the energy of the $`\psi _3`$ states while leaving the $`\psi _2`$ states unchanged. One thereby obtaines an effective $`S=1`$ Heisenberg chain with a Haldane gap at $`\pi /(2b)`$.

In the following we will focus on the first parameter regime where $`\psi _1`$ is the only groundstate. For an isolated cluster there are two low energy triplet excitations $`\psi _3`$ and $`\psi _4`$. To calculate their dispersion along b we perform a strong-coupling expansion  around the isolated cluster limit treating

$$H_1=J_2\underset{n}{}𝐒_{1,n}𝐒_{2,n+1}$$
(8)
as a perturbation. For the moment we neglect the inter-chain coupling $`J_3`$ which we assume to be significantly smaller than $`J`$ due to the longer exchange path along a. We have calculated series up to order 7 in $`J_2/J_1`$ where the largest system taken into account contains $`L=32`$ spins.

The two triplet dispersions are well seperated for large values of $`J^{}`$ as shown in Fig. 2. Here the obtained series are very well converged already in second order. Our results are consistent with those of the reported exact diagonalization and DMRG calculations, whereas the results of the linearized Holstein-Primakov approximation (LHP) used in the cluster-operator theory  disagree slightly for momenta in the region around $`k=0`$.

The perturbative Hamiltonian $`H_1`$ strongly intermixes the two magnon excitations $`\psi _3`$ and $`\psi _4`$. For small values of the cluster exchange $`J^{}`$ and the dimerization $`\delta `$ we find that the two energy bands are very close by for intermediate momenta $`0<k_y<\pi /(2b)`$ as shown in Fig. 3.

We have calculated effective Hamiltonians for the two excitations seperately as well as a combined effective Hamiltonian treating the excitations on the same footing. We thereby consider the repulsive interaction between the two energy bands. While the first approach suffers a break-down of the perturbation expansion due to small energy denominators in momentum regions where the two mixing magnon excitations are nearly degenerate, it allows to assign the nature of the excitation at $`k_y=\pi /(2b)`$. For example, we find that for $`J^{}=1.1J_1`$ and $`\delta =0.5`$ the lower energy at $`k_y=0`$ corresponds to a $`\psi _3`$-excitation, whereas at $`k_y=\pi /(2b)`$ the lower excitation corresponds to a $`\psi _4`$-excitation. In Fig. 3 we have used Dlog Padé approximants which extrapolate the calculated finite series to flatten out the occuring singularities (dashed lines).

The second approach allows to explicitely calculate the mixing between the two excitation branches. We find that there is strong band repulsion for the whole parameter range. For those parameter sets where in the first approach the extrapolated dispersions cross we now find two well separated branches, but the nature of the excitation changes depending on the momentum.

Neutron scattering experiments observe the spin gap at the antiferromagnetic point $`k_y^{AF}=\pi /b`$ and the zone center $`k_y^{ZC}=0`$, which would correspond to a $`\psi _3`$-excitation in the spin-cluster model. This assignment enables us to determine the ratio of $`\mathrm{\Delta }_{max}`$ at $`k=\pi /(2b)`$ to the gap $`\mathrm{\Delta }_{min}`$ at $`k=0`$ in order to clarify wether an observed gap value of around 10 meV is consistent with an estimate of 40 to 60 meV for the spin exchange $`J`$. In Fig. 4 we show the calculated values at the respective momenta for $`J^{}=0.75J_1`$ as a function of dimerization $`\delta `$. For small values of $`\delta `$ the results of the strong coupling expansion are less reliable, but it seems that a ratio of 4 does not disagree with our results. A tentatively estimated parameter set of $`J^{}=0.66J_1`$ and $`\delta =0.05`$ would give a ratio of around 3 and a spin gap of around $`0.25J_1`$ which was doubted in a previous theoretical analysis .

Nevertheless, we point out that the shape of the $`\psi _3`$-dispersion is rather flat in the vicinity of $`k_y=0`$ and $`k_y=\pi /b`$ which is due to the strong band repulsion. This seems to contradict the experimental observations of a steep ascent . Further we note that for these parameters the minimum of the $`\psi _4`$-excitation at $`k_y=\pi /(2b)`$ is of comparable size to the actual spin gap, but has not been reported by neutron scattering experiments.

The leading contribution to the dispersion of the low-lying $`\psi _3`$-magnon excitation along a is given by the spin exchange mediated by an interaction $`J_3`$ between neighboring spin-clusters (see Fig. 1):

$`ϵ_{ab}(𝐤_𝐱,𝐤_𝐲)`$ $`=`$ $`ϵ_b(𝐤_𝐲)`$ (10)
$`+{\displaystyle \frac{J^{}J_3^2}{3J_1(J_12J^{})}}\mathrm{cos}(𝐤_𝐱𝐚)\mathrm{cos}(𝐤_𝐲𝐛).`$
The spin-cluster model inherently produces a leading periodicity of $`2\pi /a`$ for the dispersion along a. This corresponds to the periodicity observed in INS experiments  and is consistent with a primitive unit cell of area $`2ab`$ as reported by structural x-ray investigations  taking into account the $`\pi /b`$ periodicity along b. The $`\psi _3`$-magnon on an isolated cluster consists of a singlet state $`s_{12}`$ along the $`b`$-axis bond. We therefore expect a strong coupling to scattering neutrons at the antiferromagnetic point $`k_y^{AF}=\pi /b`$ and only a strongly suppressed signal in the vicinity of the zone center at $`k_y^{ZC}=0`$. According to (10) the modulation of the magnon dispersion along a is out of phase for these choices of $`k_y`$.

Recent neutron scattering experiments  report the observation of two close by, but well separated, out of phase magnon branches. The spin-cluster model at hand gives only one low lying magnon branch with the observed periodicity. This excludes a simple spin-Peierls scenario to explain the occurence of $`two`$ out of phase magnon branches, e. g. folding back a single magnon branch with double periodicity as it was suggested for a zig-zag model in .

A way of explaining the occurence of two close by magnon branches in this model is to consider an anisotropic exchange interaction. An xxz-anisotropy could lift the triplet degeneracy in a single branch and a doublet branch. Experimentally this splitting of a single triplet branch should result in a 1:2 ratio of neutron scattering intensities which has not been reported . Further, a magnetic field would cause the doublet line to split which has not been confirmed by optical spectroscopy .

The investigation of the spin-cluster model reveals some new aspects that should be covered by future neutron scattering experiments, namely the experimental evidence of asymmetric couplings and a verification of the basic symmetries found in x-ray scattering.

Beside a careful investigation of the scattering intensities of the two magnon branches, polarized neutron scattering experiments could give evidence for the splitting of a single magnon line, thereby proving the existence of anisotropic couplings.

The verification of the basic symmetries by means of neutron scattering experiments is experimentally by far less sophisticated. The spin-cluster model is symmetric under reflections along the mirror planes $``$a and $``$b. Accordingly, the obtained dispersion $`ϵ_{ab}(k_x,k_y)`$ is symmetric under transformations of $`k_xk_x`$ and $`k_yk_y`$. The experimental data of the dispersion along a for $`k_y=0`$ and $`k_y=\pi /b`$ seem to be symmetric under the reflection $`k_xk_x`$. Nevertheless we point out that scanning along an arbitrary value of $`k_y`$ will allow to distinguish between models obeying double reflection symmetry and inversion symmetry. For the latter we generally expect an unsymmetric dispersion for intermediate $`k_y`$, whereas for models with double reflection symmetry we expect a cosine modulation of the amplitude of a symmetric dispersion along a as given in (10).

For a single spin-cluster, there is one low-lying singlet excitation $`\psi _2`$ which is degenerate with the triplet excitation $`\psi _3`$. For vanishing inter-chain coupling $`J_3`$ the Hamiltonian (4) is symmetric under a local interchange of $`𝐒_{3,n}`$ and $`𝐒_{4,n}`$. The perturbation operator $`H_1`$ also conserves this local symmetry. A direct product state of $`\psi _1`$ states which are even under this symmetry and a $`\psi _2`$ excitation at some arbitrary cluster which is odd under this symmetry couples to a variety of states with the same local symmetries, but does not allow the singlet excitation $`\psi _2`$ to move. Though the energy of this excitation will be changed, it will not gain any dispersion. As a consequence the original degeneracy with the triplet excitation $`\psi _3`$ is lifted. Neglecting the interaction along the $`a`$-axis we have calculated the energy of the singlet $`\psi _2`$ up to order 10 in $`J_2/J_1`$. It turns out that the ratio of the obtained energy to the gap of the elementary triplet excitation is very consistent with the expected value of 1.6 for the $`higher`$ singlet excitation at 107 cm-1 as measured in Raman spectroscopy.

To explain the occurence of a low lying Raman excitation at 66 cm-1 (8.3 meV)  we have estimated the binding energies of 2-magnon singlet bound states build of the elementary triplet excitations $`\psi _3`$ and $`\psi _4`$. We find that in leading order there is no substantial renormalization of these energies and we conclude that these bound states are close to the 2-magnon continuum at $``$ 132 cm-1 and are not sufficient to explain the occurence of the low lying Raman excitation. Recent ESR studies show evidence for a Dzyaloshinskii-Moriya interaction below 20 K . The inclusion of spin-orbit coupling might explain the observation of a Raman excitation degenerate to the spin gap.

In conclusion, we have calculated the magnetic excitations of a spin-cluster model. We find only partial agreement with the experimentally observed spectrum. Along the crystallographic $`b`$-axis there are two strongly intermixing magnon bands in the parameter regime relevant for NaV2O5. Due to strong band repulsion we find that the lower magnon branch exhibits a weaker dispersion than experimentally observed. Further, the purely magnetic model leads to only one magnon branch with the observed periodicity along the $`a`$-axis. We find one low lying singlet state which matches the energy of one of the observed Raman excitations. While the prevailing models for the low temperature phase of NaV2O5 are inversion symmetric, the spin-cluster model obeys double reflection symmetry. To generally distinguish between these models we propose further experiments scanning the magnon dispersions along a for arbitrary values of $`k_y`$.

We thank Girsh Blumberg for many valuable discussions. ST was supported in part by the German National Merit Foundation.