# Magnetic Properties of Quantum Ferrimagnetic Spin Chains: Ferrimagnetism ≈ Ferromagnetism + Antiferromagnetism ?

## Abstract

Magnetic susceptibilities of spin-$`(S,s)`$ ferrimagnetic Heisenberg chains are numerically investigated. It is argued how the ferromagnetic and antiferromagnetic features of quantum ferrimagnets are exhibited as functions of $`(S,s)`$. Spin-$`(S,s)`$ ferrimagnetic chains behave like combinations of spin-$`(Ss)`$ ferromagnetic and spin-$`(2s)`$ antiferromagnetic chains provided $`S=2s`$.

PACS numbers: 75.10.Jm, 75.40.Mg, 65.50.$`+`$m

Quantum behavior of mixed-spin systems is one of the hot topics and a recent progress in the theoretical understanding of it deserves special mention. In contrast with pioneering calculations  in the 1980s, the current vigorous argument might more or less be motivated by the Haldane conjecture  in that it covers not only ferrimagnetism but also mixed-spin antiferromagnetism. As coexistent spins of different kinds do not necessarily result in magnetic ground states, it remains a stimulative problem there whether the system is massive or massless. Actually various mixed-spin chains  and ladders  with singlet ground states have also been discussed extensively via the nonlinear-$`\sigma `$-model technique with particular emphasis on the competition between massive and massless phases. On the other hand, an arbitrary alignment of alternating spins $`S`$ and $`s`$, which is described by the Hamiltonian

$$=\underset{j}{}\left(J_1𝑺_j𝒔_j+J_2𝒔_j𝑺_{j+1}\right),$$
(1)   
shows ferrimagnetism instead of antiferromagnetism and thus has gapless excitations from the ground state.

Chemical explorations into ferrimagnetic chain compounds have vigorously been reported so far. In an attempt to obtain bimetallic complexes including one-dimensional systems, CuMn(S<sub>2</sub>C<sub>2</sub>O<sub>2</sub>)<sub>2</sub>(H<sub>2</sub>O)<sub>3</sub>$``$4.5H<sub>2</sub>O  was first synthesized. Since then numerous bimetallic chain compounds  were systematically synthesized and measured. In the series of investigations, the smaller spin $`s`$ was fixed to $`1/2`$ and the larger spin $`S`$ was changed from $`1/2`$ to $`5/2`$ featuring several important concepts. One of their main interests was the achievement of a ferromagnetic interaction between nearest-neighbor metal ions, namely, the design of molecular-based ferromagnets. Therefore quantum ferrimagnetism was not necessarily the main subject there. Though there also appeared theoretical investigations  in close contact with experiments, the argument was restricted to the spin combinations $`(S,1/2)`$ and the larger spin $`S`$ was sometimes treated as classical.

In such circumstances, several renewed interests , have recently been introduced into the field. Alcaraz and Malvezzi  predicted the universal low-energy physics of anisotropic ferrimagnetic chains and the distinct behavior of isotropic ones. Kuramoto  discussed critical properties of the model in a field showing its magnetization curve with a plateau. Maisinger et al.  revealed the field-induced double-peak structure of the specific heat. Another noteworthy subject, which is the main interest here, is the coexistence of the ferromagnetic and antiferromagnetic features in quantum ferrimagnets. The author et al. pointed out in their recent study  on the model (1) with $`(S,s)=(1,1/2)`$ that at low temperatures the model acts as a ferromagnet, while at intermediate temperatures it behaves like a gapped antiferromagnet. In this article, we quantitatively verify to what extent this scenario is valid discussing various combinations of $`(S,s)`$. Even though there is an ambiguous belief that the $`(S,s)=(1,1/2)`$ case is representative of all the Heisenberg ferrimagnetic chains, it is not yet really clear whether or how the quantum behavior of the model depends on the constituent spins. We here show that the magnetic behavior of spin-$`(S,s)`$ quantum ferrimagnets is regarded as the combination of those of spin-$`(Ss)`$ ferromagnets and spin-$`(2s)`$ antiferromagnets provided $`S=2s`$. The dual aspect is qualitatively generic to all the Heisenberg ferrimagnets, but those with $`S=2s`$ should quantitatively be distinguished from the others.

We investigate the zero-field magnetic susceptibility $`\chi `$ of the model (1) of $`N`$ elementary cells with $`J_1=J_2=J`$ under the periodic boundary condition. We take $`\mu _B`$ as the Bohr magneton and set the $`g`$ factors of both spins $`S`$ and $`s`$ equal to $`g`$. We assume that $`S>s`$. The numerical procedure of the quantum Monte Carlo method employed has been detailed elsewhere . Since the correlation length of the system is considerably small , the thermal quantities in general show no significant size dependence. We have calculated the chains of $`N=24`$ and $`N=32`$, but we find no difference beyond the numerical uncertainty between them in the temperature region treated. On the other hand, for the sake of argument, we calculate the susceptibilities of Heisenberg ferromagnetic and antiferromagnetic rings as well, where we consider chains of $`N`$ spins.

We show in Fig. 1 temperature dependences of the product $`\chi T`$ at various combinations of $`(S,s)`$. We note that here $`\chi T`$ shows a minimum in its temperature dependence. Although the low-temperature divergence, which is proportional to $`T^1`$, is reminiscent of the ferromagnetic susceptibility, $`\chi T`$ approaches its paramagnetic behavior $`[S(S+1)+s(s+1)]/3`$ showing the antiferromagnetic increase. Considering that $`\chi T`$ is a monotonically decreasing function in ferromagnets, while a monotonically increasing function in antiferromagnets, the present observations may be regarded as a ferromagnetic-antiferromagnetic crossover.

This mixed feature is a consequence of the dual structure of excitations . Quantum ferrimagnets exhibit two distinct branches of elementary excitations, one of which reduces the magnetization $`M_j(S_j^z+s_j^z)`$ and is thus called ferromagnetic, and the other of which enhances that and is thus called antiferromagnetic. The lowest-order spin-wave approach  to the model (1) with $`J_1=J_2=J`$ indeed results in two dispersions

$$\omega _k^{}=J\left[\sqrt{(Ss)^2+4Ss\mathrm{sin}^2(ak)}(Ss)\right],$$
(2)   
with the lattice spacing $`a`$, which are quadratic at small $`k`$’s and gapped from the ground state, respectively. Another naive but suggestive calculation  is the perturbation from the decoupled-dimer limit, where the ground state and its elementary excitations are trivially obtained (Fig. 2). When we turn on the exchange interaction between the dimers, the localized excitations begin to hop to neighboring unit cells and become dispersive. In the case of $`(S,s)=(1,1/2)`$, for instance, setting $`J_1`$ and $`J_2`$ for $`J`$ and $`\delta J`$, respectively, we obtain

$`\omega _k^{}`$ $`=`$ $`{\displaystyle \frac{4}{9}}J\delta [1\mathrm{cos}(2ak)]+O(\delta ^2),`$ (3)   
$`\omega _k^+`$ $`=`$ $`{\displaystyle \frac{3}{2}}J+{\displaystyle \frac{1}{18}}J\delta [712\mathrm{cos}(2ak)]+O(\delta ^2).`$ (4)   
For an arbitrary combination of $`(S,s)`$, the similar argument ends up with qualitatively the same dispersions.

Based on this scenario for low-lying excitations, we propose in Fig. 3 an idea of decomposing ferrimagnets into ferromagnets and antiferromagnets, where we let the decoupled dimers and the Affleck-Kennedy-Lieb-Tasaki valence-bond-solid states  symbolize ferrimagnets and integer-spin gapped antiferromagnets, respectively. Now we are led to expect spin-$`(S,s)`$ ferrimagnets to behave like combinations of spin-$`(2s)`$ antiferromagnets and spin-$`(Ss)`$ ferromagnets. In this context, we compare in Fig. 4 the ferrimagnetic susceptibilities with those of ferromagnets and antiferromagnets. Surprisingly, the sum of the spin-$`(2s)`$ antiferromagnetic and spin-$`(Ss)`$ ferromagnetic susceptibilities excellently reproduces the spin-$`(S,s)`$ ferrimagnetic behavior on condition that $`S=2s`$, whereas such a naive relation does not stand up in the other cases. Considering several suggestive calculations, we may be convinced of the present observations.

First, the high-temperature paramagnetic behavior distinguishes the $`S=2s`$ cases from the others. At high enough temperatures, we should obtain the paramagnetic susceptibilities as

$`{\displaystyle \frac{k_\mathrm{B}T\chi ^{(S,s)\text{-}\mathrm{ferri}.}}{Ng^2\mu _\mathrm{B}^2}}={\displaystyle \frac{1}{3}}\left[S(S+1)+s(s+1)\right],`$ (5)   
$`{\displaystyle \frac{k_\mathrm{B}T\chi ^{(Ss)\text{-}\mathrm{ferro}.}}{Ng^2\mu _\mathrm{B}^2}}={\displaystyle \frac{1}{3}}(Ss)(Ss+1),`$ (6)   
$`{\displaystyle \frac{k_\mathrm{B}T\chi ^{(2s)\text{-}\mathrm{antiferro}.}}{Ng^2\mu _\mathrm{B}^2}}={\displaystyle \frac{1}{3}}2s(2s+1).`$ (7)   
It is interesting that we have an equality $`\chi ^{(S,s)\text{-}\mathrm{ferri}.}=\chi ^{(Ss)\text{-}\mathrm{ferro}.}+\chi ^{(2s)\text{-}\mathrm{antiferro}.}`$ just in the cases of $`S=2s`$.

Second, the spin-wave dispersions (2) give us a useful piece of information. The small-momentum ferromagnetic excitations must dominate the low-temperature thermodynamics and therefore the curvature of their dispersion is of great interest. Let us recall that spin-$`S`$ ferromagnetic Heisenberg chains exhibit the dispersion of single-magnon excitations,

$$\omega _k=2JS(1\mathrm{cos}ka).$$
(8)   
Defining the curvature $`v`$ for quadratic dispersions as $`\omega _{k0}=v(\stackrel{~}{a}k)^2`$ with the unit-cell length $`\stackrel{~}{a}`$, we obtain

$`v^{(S,s)\text{-}\mathrm{ferri}.}={\displaystyle \frac{Ss}{2(Ss)}}J,`$ (9)   
$`v^{(Ss)\text{-}\mathrm{ferro}.}=(Ss)J.`$ (10)   
Here we learn that $`v^{(S,s)\text{-}\mathrm{ferri}.}=v^{(Ss)\text{-}\mathrm{ferro}.}`$ provided $`S=2s`$. Though the coincidence holds within the lowest-order spin-wave theory, it looks meaningful.

Finally, we point out that the modified spin-wave treatment  of spin chains is also suggestive in our argument. The modified spin-wave theory was first introduced by Takahashi  for quantum ferromagnets. Imposing a constraint on the magnetization, he obtained the low-temperature susceptibilities of spin-$`S`$ ferromagnetic chains as

$$\frac{J\chi ^{S\text{-}\mathrm{ferro}.}}{N(g\mu _\mathrm{B})^2}=\frac{2S^4}{3}t^2\frac{\zeta (\frac{1}{2})}{\sqrt{\pi }}S^{5/2}t^{3/2}+\left[\frac{\zeta (\frac{1}{2})}{\sqrt{\pi }}\right]^2\frac{S}{2}t^1+O(t^{1/2}),$$
(11)   
where $`t=k_\mathrm{B}T/J`$ and $`\zeta (z)`$ is Riemann’s zeta function. Equation (11) was shown to precisely agree with the thermodynamic Bethe-ansatz calculation  in the case of $`S=1/2`$. On the other hand, the author and Fukui  have recently developed the scheme for quantum ferrimagnets. They constructed the thermodynamics based on the dispersions (2) and obtained the expression for the susceptibility,

$$\frac{J\chi ^{(S,s)\text{-}\mathrm{ferri}.}}{N(g\mu _\mathrm{B})^2}=\frac{Ss(Ss)^2}{3}t^2(Ss)^{1/2}(Ss)^{3/2}\frac{\zeta (\frac{1}{2})}{\sqrt{2\pi }}t^{3/2}+(Ss)\left[\frac{\zeta (\frac{1}{2})}{\sqrt{2\pi }}\right]^2t^1+O(t^{1/2}).$$
(12)   
For ferrimagnets the constraint is not so trivial as for ferromagnets. However, as far as the low-temperature behavior is concerned, we obtain the universal description regardless of the artificial constraint. Equation (12) is thus reliable to a certain extent. Now we again encounter the surprising coincidence between the two results, $`\chi ^{(S,s)\text{-}\mathrm{ferri}.}=\chi ^{(Ss)\text{-}\mathrm{ferro}.}`$, provided $`S=2s`$.

Thus we have learned that several analytic treatments, as well as numerical calculations, distinguish ferrimagnetic chains with $`S=2s`$ from the others. We conclude an approximate sum rule among ferrimagnets, ferromagnets, and antiferromagnets on condition that $`S=2s`$:

$$\chi ^{(S,s)\text{-}\mathrm{ferri}.}=\chi ^{(Ss)\text{-}\mathrm{ferro}.}+\chi ^{(2s)\text{-}\mathrm{antiferro}.}.$$
(13)   
Equation (13) well holds in a wide region of temperature except for the ferromagnetic-to-antiferromagnetic transitional period. Both ferromagnetic and antiferromagnetic features generically lie in quantum ferrimagnets, to be sure, but the quantitative identity of them is established only in the cases of $`S=2s`$. For $`S>2s`$ quantum ferrimagnets are rather ferromagnetic than antiferromagnetic, whereas for $`S<2s`$ vice versa. In fact we find in Fig. 1 that $`\chi T`$ shows a relatively significant low-temperature divergence for $`S>2s`$, while it increases relatively rapidly at intermediate temperatures for $`S<2s`$. Brand-new experiments  are in progress under the current interest. We hope that the second wave of close collaboration between theoretical and experimental investigations will be brought about.

It is a pleasure to thank T. Fukui, H.-J. Mikeska, and S. K. Pati for fruitful discussions. This work was supported by the Japanese Ministry of Education, Science, and Culture through Grant-in-Aid No. 09740286 and by the Okayama Foundation for Science and Technology. The numerical computation was done in part using the facility of the Supercomputer Center, Institute for Solid State Physics, University of Tokyo.