# Spin-Peierls Transition in CuGeO3: Critical, Tricritical or Mean Field?

## I Introduction

The spin-Peierls transition corresponds to the dimerization of a one-dimensional S = $`\frac{1}{2}`$ antiferromagnetic chain coupled to a three dimensional elastic medium -. Until relatively recently, spin-Peierls transitions had only been observed in organic charge transfer compounds such as copper bisdithiolene (TTF-CuBDT) -. Experimental information obtainable in such systems has been limited both by the size of available single crystals and by the sensitivity of these materials to damage by x-rays or electrons. Nevertheless, some important information on the spin-Peierls phase transition has been obtained in a number of different organic materials. Interestingly, in most, if not all cases, the data are consistent with a simple BCS-type mean field transition -.

Much more complete experimental work on the spin-Peierls transition has been made possible by the discovery that a structurally simple, inorganic chain compound copper germanate (CuGeO<sub>3</sub>) undergoes a spin-Peierls transition at a transition temperature around 14K . The crystal structure of CuGeO<sub>3</sub> is orthorhombic, space group Pbmm, with a unit cell of dimensions $`a=4.81`$ Å, $`b=8.47`$ Å and $`c=2.94`$ Å at room temperature . The Cu<sup>2+</sup> ion carries a spin $`S=\frac{1}{2}`$ and forms a (CuO<sub>2</sub>) chain with the neighboring Cu<sup>2+</sup> ions along the $`c`$-axis direction. The successive Cu<sup>2+</sup> S = $`\frac{1}{2}`$ spins are antiferromagnetically coupled through the superexchange interactions via the bridging oxygen atoms. Below the spin-Peierls transition temperature, $`T_{SP}`$, the dimerization of Cu-Cu pairs along the $`c`$-axis direction, accompanied by shifts of the bridging oxygen atoms in the $`ab`$ plane, gives rise to superlattice reflections at the $`(\frac{h}{2},k,\frac{l}{2})`$ ($`h,l`$: odd and $`k`$: integer) reciprocal-lattice positions . These have been observed in electron diffraction , x-ray , and elastic neutron scattering  experiments. Using coarse resolution x-ray diffraction techniques, Pouget et al.  have measured the pretransitional thermal lattice fluctuations whose correlation lengths diverge anisotropically with decreasing temperature in a manner consistent with mean field theory. These same fluctuations have been studied at high resolution using synchrotron x-ray diffraction techniques by Harris et al. . These latter authors observe within about 1K of $`T_{SP}`$ large length scale fluctuations with characteristic length scales about an order of magnitude longer than those characterizing the bulk critical fluctuations.

In spite of this large amount of work, it is still not agreed whether the observed transition behavior reflects mean field or critical behavior. Extant models include: a) tricritical to 3D Ising crossover behavior ; b) mean field behavior ; c) 3D XY with corrections to scaling , and, most exotically, d) a 2D XY to 3D XY crossover as $`T_{SP}`$ is approached . Harris et al.  first argued that because of the one-component nature of the dimerization order parameter for a spin-Peierls phase transition, asymptotically the transition must be in the 3D Ising universality class. They argued further, that because of the coupling to the elastic strains, the precritical behavior should be tricritical-like. Similar conclusions, albeit based on different physical reasoning, were arrived at later by Werner and Gros . Proponents of 3D XY behavior typically argue that the copper and oxygen displacements are independent thence yielding a two-component order parameter . Implicitly, Harris et al.  assume that all of the atomic displacements accompanying the spin-Peierls transition are linearly coupled thence reducing the system to a one-component order parameter. The 3D critical behavior models seem to be supported by measurements of the order parameter  which for reduced temperatures $`2\times 10^3<1T/T_{SP}5\times 10^2`$ exhibits power law behavior $`(1T/T_{SP})^\beta `$ with $`\beta =0.33\pm 0.02`$, in good agreement with both 3D Ising and XY values of $`\beta =0.325`$ and 0.345 respectively . The heat capacity data are equally well described by a 3D critical behavior model (Ising or XY) and by a mean field model with Gaussian fluctuations .

In this paper we present an alternative model for CuGeO<sub>3</sub>, namely a Landau-Ginzburg model incorporating a tricritical to mean field crossover. As we shall show, this model describes all available data very well with few adjustable parameters. The format of this paper is as follows. In Section II we introduce the model including its genesis in studies of critical phenomena in thermotropic liquid crystals systems. Section III presents an analysis of the available data for CuGeO<sub>3</sub> using this model. Finally, in Section IV we give a summary, our conclusions and suggestions for future experiments.

## II The Model

The conundrum described above for CuGeO<sub>3</sub> is reminiscent of a similar divergence of views which occurred in the interpretation of experiments on smectic A - smectic C phase transitions in thermotropic liquid crystal systems -. In particular, in that case, measurements of the tilt order parameter  typically reveal power law behavior $`\varphi (1T/T_{AC})^\beta `$ over the temperature range $`5\times 10^5<(1T/T_{AC})<5\times 10^3`$ with $`\beta =0.36\pm 0.02`$. However, this divergence of views was resolved by Huang and Viner  and Birgeneau et al.  who showed that all of the data including the heat capacity, order parameter, and tilt susceptibility, were consistent with the predictions of a simple Landau model with an anomalously large 6th order term. Clearly, it is of interest to carry out a similar analysis for the available data for the spin-Peierls transition in CuGeO<sub>3</sub>.

For the Landau-Ginzburg model the free energy is given by

$$F=a\tau \varphi ^2+b\varphi ^4+c\varphi ^6\mathrm{}.+\frac{1}{2m_\alpha }|_\alpha \varphi |^2$$
(1)   
where $`\tau =T/T_c1`$.

With $`\tau _0=b^2/ac`$, standard calculations yield for the order parameter, $`\varphi `$, the specific heat, $`C`$, the susceptibility, $`\chi `$, and the correlation length, $`\xi _\alpha `$,:

$`\varphi `$ $`=`$ $`(b/3c)^{1/2}[(13\tau /\tau _0)^{1/2}1]^{1/2}\tau <0`$ (2)   
$`C`$ $`=`$ $`\{\begin{array}{cc}0\hfill & \hfill \tau >0\\ (a^2T/2bT_c^2)(13\tau /\tau _0)^{1/2}\hfill & \hfill \tau <0\end{array}`$ (5)   
$`\chi `$ $`=`$ $`1/2a\tau \tau >0`$ (6)   
$`\xi _\alpha `$ $`=`$ $`(2am_\alpha \tau )^{1/2}\tau >0`$ (7)   
with similar expressions for $`\tau <0`$ for $`\chi `$ and $`\xi `$. Eq. (2) and (3) are conveniently rewritten in the form

$`\begin{array}{cccc}\varphi \hfill & =\hfill & \varphi _0\begin{array}{cc}\left[\left(1+3\frac{T_{SP}T}{T_{SP}T_{CR}}\right)^{1/2}1\right]^{1/2}\hfill & \tau <0\hfill \end{array}\hfill & \end{array}`$ (10)   
$`\begin{array}{cccc}C\hfill & =\hfill & \{\begin{array}{cc}0\hfill & \tau >0\hfill \\ C\mathrm{\_}T\left(1+3\frac{T_{SP}T}{T_{SP}T_{CR}}\right)^{1/2}\hfill & \tau <0\hfill \end{array}\hfill & \end{array}`$ (14)   
where $`T_{CR}`$ is the crossover temperature from tricritical to mean field behavior. We note that in the above expressions the exponents are fixed and only the amplitudes and the two temperatures, $`T_{SP}`$ and $`T_{CR}`$, are variable. A log-log plot of Eq. (6) reveals that for the order parameter $`\varphi `$ the effective exponent $`\beta `$ crosses over gradually from $`\frac{1}{4}`$ to $`\frac{1}{2}`$ as $`T`$ varies from less than to greater than $`T_{CR}`$. In the smectic A - smectic C case the measurements span $`T_{CR}`$ and accordingly intermediate exponents, $`\beta 0.36`$, are found even though the actual transition is mean-field-like for temperatures in the immediate vicinity of $`T_{AC}`$ .

## III Analysis

We now apply this tricritical–mean field crossover model to CuGeO<sub>3</sub>. The first test is $`T_{SP}`$ itself or, more precisely, the ratio of the spin gap, $`\mathrm{\Delta }`$, to $`T_{SP}`$. In the mean field theory of Pytte , the spin-Peierls transition is BCS-like so that in the weak coupling limit $`2\mathrm{\Delta }/T_{SP}=3.5`$. In the charge transfer salts TTF - CuBDT , TTF - AuBDT , MEM - (TCNQ)<sub>2</sub> , and SBTTF - TCNQCl<sub>2</sub>  this ratio is found to be 3.5, 3.7, 3.1 and $``$ 3.5 respectively, in good agreement with the BCS value. Critical fluctuations, either Ising or XY in character, would act to increase this ratio. For CuGeO<sub>3</sub>, $`\mathrm{\Delta }=24.5`$K and $`T_{SP}14`$K implying $`2\mathrm{\Delta }/T_{SP}=3.5`$, consistent with a BCS mean field theory description . At the minimum, this value for $`2\mathrm{\Delta }/T_{SP}`$ argues against any quantitatively important effect of critical fluctuations on $`T_{SP}`$ in CuGeO<sub>3</sub>.

The behavior of the order parameter in CuGeO<sub>3</sub> is of particular importance since this observable appears to provide the strongest evidence for true critical rather than mean field or tricritical behavior. A number of groups have reported measurements of the temperature dependence of the order parameter in CuGeO<sub>3</sub> . The measured phase transition temperature $`T_{SP}`$ varies between 13.3K and 14.6K in different samples. Nevertheless, near-universal behavior is observed for the order parameter provided that it is plotted as a function of the reduced temperature $`T/T_{SP}`$. As noted above, fits of the order parameter $`\varphi (T/T_{SP})`$ for $`1T/T_{SP}<0.05`$ to a single power law $`\varphi (1T/T_{SP})^\beta `$ all yield values of $`\beta =0.33\pm 0.02`$. As discussed by Gaulin and co-workers , inclusion of a correction-to-scaling multiplicative factor $`(1+B|\tau |^\delta )`$ in the expression for $`\varphi `$ both improves the goodness of fit and, not surprisingly, extends the range of validity of the fit.

We show in Fig. 1 our own measurements of the order parameter squared in a sample of CuGeO<sub>3</sub> with $`T_{SP}=14.6`$K. These data are consistent with those measured by both ourselves and other groups in a variety of samples . Fits to a single power law for $`\tau <0.04`$ yield $`\beta =0.314\pm 0.01`$. However, as noted by Harris et al.  and as may be seen in Fig. 1, the data fall significantly below the power law curve for $`\tau >0.04`$. We show, in addition, in Fig. 1 the results of a fit to the tricritical to mean field crossover form, Eq. (6). This fit has only three adjustable parameters, $`\varphi _0^2`$, $`T_{CR}`$ and $`T_{SP}`$. This is the same number of parameters as those in the single power law fits discussed above and two less than the number of adjustable parameters in fits to a power law with corrections-to-scaling with both $`B`$ and $`\delta `$ varied. (We note that Lumsden et al.  fix $`\delta =1/2`$ whereas Lorenzo et al. allow $`\delta `$ to vary; the latter group find an optimum fit for $`\delta 1`$). It is evident that Eq. (6) describes the order parameter data extremely well over the complete range of temperatures. The fit yields $`\tau _{CR}=1T_{CR}/T_{SP}=0.006\pm 0.001`$ implying that the crossover from tricritical to mean field behavior occurs at a quite small reduced temperature.

We now discuss the energy gap $`\mathrm{\Delta }`$. Using a simple scaling ansatz, Cross and Fisher  argue that $`\mathrm{\Delta }\varphi ^{2/3}`$. We show in Fig. 2 the data of Lorenzo et al.  for the magnetic energy gap for $`T<T_{SP}`$ in a sample of CuGeO<sub>3</sub> with $`T_{SP}=14.4`$K. In part because of the apparent jump of $`\mathrm{\Delta }(T)`$ at $`T_{SP}`$, Lorenzo et al.  interpret these data as indicating a 2D XY Kosterlitz-Thouless transition . In fact, these data are readily explained using the model of Cross and Fisher  together with the tricritical-mean field crossover form for $`\varphi `$, Eq. (6). In this case we hold $`T_{SP}`$ fixed at $`T_{SP}=14.4`$K and set $`\tau _{CR}=0.006`$ as determined above so that there is only one adjustable parameter, the overall amplitude $`\mathrm{\Delta }(0)`$. The result so-obtained is shown in Fig. 2. It is evident that the tricritical-mean field model with $`\mathrm{\Delta }(T)\varphi ^{2/3}`$ describes the measured gap energy $`\mathrm{\Delta }(T)`$ extremely well over a wide range of temperatures with only one adjustable parameter. Indeed, this is by far the best test to-date of the Cross-Fisher model. We should note that this model cannot explain the inferred pseudogap above T<sub>SP</sub> . However, the “pseudogap” is deduced using a heuristic line-shape analysis which lacks a firm theoretical basis.

The specific heat in CuGeO<sub>3</sub> has proven to be the most difficult thermodynamic quantity to interpret unambiguously . This is, in part, because of the extreme sensitivity of the specific heat near $`T_{SP}`$ to sample inhomogeneities and, in part, because of the inevitable large number of adjustable parameters required to describe the critical specific heat in any physically relevant model. Fig. 3 shows high resolution magnetic specific heat $`(C_M)`$ data for a sample of CuGeO<sub>3</sub> with $`T_{SP}=14.24`$K from Lasjaunias and coworkers . Hegman et al.  have carried out an extensive analysis of these data using both a mean field “BCS plus Gaussian fluctuation” model and a critical behavior model. They find that both models describe $`C_M`$ quite well in the immediate vicinity of $`T_{SP}`$, albeit at the cost of a rather large number of adjustable parameters. The critical behavior model fits give a value for the specific heat exponent, $`\alpha `$, near 0. On the other hand, the Gaussian fluctuation analysis implies that the true critical behavior is confined to the region $`|\tau |<0.0006`$.

Given the uncertainties connected with the fits described above, the best one can hope for is to determine whether or not the tricritical-mean field crossover model is consistent with the experimental results for $`C_M`$ shown in Fig. 3. First, it is evident that Eq. (7) will be inadequate since one must, at the minimum, include Gaussian fluctuations above $`T_{SP}`$. We therefore include the fluctuations above T<sub>SP</sub> in the simplest way possible by replacing Eq. (7) by

$$\begin{array}{ccc}C_M\hfill & \hfill =& \{\begin{array}{cc}C_M^+T\left(1+3\frac{TT_{SP}}{T_{SP}T_{CR}}\right)^{1/2}+\gamma T\hfill & \hfill \tau >0\\ C_M^{}T\left(1+3\frac{T_{SP}T}{T_{SP}T_{CR}}\right)^{1/2}+B\mathrm{\_}\hfill & \hfill \tau <0\end{array}\hfill \end{array}$$
(15)   
where $`\gamma T`$ is the regular linear term for a 1D Heisenberg antiferromagnet and $`B\mathrm{\_}`$ is the background term below $`T_{SP}`$. The background $`B_{}`$ should, in general, be temperature dependent; however, given the narrow range of temperatures we consider, a constant background is adequate. Eq. (8) is closely similar to the BCS plus Gaussian fluctuation model considered by Hegman et al.  since the Gaussian fluctuations give rise to a $`|\tau |^{1/2}`$ contribution to $`C_M`$ both above and below $`T_{SP}`$. The solid lines in Fig. 3 correspond to fits to Eq. (8) with $`\tau _{CR}`$ fixed at 0.006 and $`C_M^+`$, $`C_M^{}`$,$`\gamma `$, $`B\mathrm{\_}`$ and $`T_{SP}`$ varied. Clearly Eq. (8) describes $`C_M`$ quite well; indeed the fit appears to be better than those for either of the models tested by Hegman et al. . The fit shown in Fig. 3 gives $`C_M^+/C_M^{}=1.1\pm 0.13`$; this ratio is expected to be non-universal so it cannot be simply interpreted. We conclude, therefore, that the tricritical-mean field crossover model describes $`C_M`$ well although not uniquely so.

Finally, we discuss the correlation length and the staggered susceptibility. Pouget et al.  have found that the correlation length over a wide temperature range follows the behavior $`\xi (T/T_{SP}1)^{1/2}`$, consistent with mean field theory; however, the number of data points in their experiment near $`T_{SP}`$ is sufficiently small that their results do not meaningfully differentiate between various theoretical models. Harris et al.  have reported a high resolution synchrotron x-ray study of the critical fluctuations above $`T_{SP}`$ in CuGeO<sub>3</sub>. They find pretransitional lattice fluctuations within 1K above $`T_{SP}`$ whose length scale is about an order of magnitude longer than those characterizing the bulk thermal fluctuations. The line-shape of the large length scale fluctuations is consistent with a Lorentzian-squared form. The measured critical exponents are $`\nu =0.56\pm 0.09`$ and $`\overline{\gamma }=2.0\pm 0.3`$ where $`\overline{\gamma }`$ is the exponent characterizing the divergence of the disconnected staggered susceptibility . The mean field predictions for these exponents are $`\nu =1/2`$ and $`\overline{\gamma }=2\gamma =2`$ whereas for 3D Ising (XY) critical behavior one expects $`\nu =0.63(0.67)`$ and $`\overline{\gamma }=2.5(2.64)`$. Thus the Harris et al.  data favor the tricritical-mean field model but 3D Ising or XY critical models are not excluded. Precise measurements of the bulk staggered susceptibility using neutrons should yield accurate values for $`\nu `$ and $`\overline{\gamma }`$ and this, in turn, would definitively choose between the models.

## IV Discussion

In summary, each of the order parameter, magnetic energy gap, specific heat, correlation length and disconnected staggered susceptibility are well-described by a simple Landau-Ginzburg model exhibiting a tricritical-mean field crossover near $`T_{SP}`$. Further, the ratio of the energy gap to $`T_{SP}`$ is consistent with the value for a BCS mean-field transition. We conclude, therefore, that CuGeO<sub>3</sub>, in common with the organic change transfer salts, exhibits a mean field spin-Peierls transition for reduced temperatures $`|\tau |>0.001`$.

The principal remaining issue is the microscopic origin of the tricritical behavior. Harris et al.  argue that this is caused by a diminution in the effective fourth order term in Eq. (1), $`b\varphi ^4`$, because of coupling to the macroscopic strain. It also seems possible that competing nearest and next-nearest neighbor exchange interactions along the chain could generate the tricritical instability . Specifically, Castilla et al.  argue that the ratio of the next nearest neighbor to nearest neighbor exchange interaction along the chain is close to the critical value for spontaneous formation of a magnetic gap independent of coupling to the lattice. Heuristically, it seems that this could generate tricritical behavior in the phase diagram. Another possible source of tricritical behavior is competition between the Néel state and the spin-Peierls state, that is, competition between the coupling of the $`S=1/2`$chain to the lattice and the interchain exchange coupling. Clearly, a multidimensional theoretical analysis of the spin-Peierls phase diagram including magnetostriction, competing intrachain exchange interactions together with the interchain magnetic and elastic coupling is required.

Of course, the mean field behavior itself in all of these spin-Peierls systems is not yet well understood. In TTF-CuBDT there is evidence for a soft phonon at very high temperatures  and Cross and Fisher  speculate that the precursive soft mode accounts for the large length scale underlying the mean field behavior. In CuGeO<sub>3</sub>, no soft phonon at all has yet been seen. Thus, the microscopic origin of the large length scale in CuGeO<sub>3</sub> remains to be elucidated.

Finally, it would be very interesting to see if the putative nearby tricritical point could be accessed by changing some variable such as pressure, uniaxial stress or doping. Masuda et al.  have shown that replacement of Cu by Mg both depresses $`T_{SP}`$ and appears to drive the spin-Peierls transition first order. The concomitant tricritical point could well account for the observed tricritical-mean field crossover in pure CuGeO<sub>3</sub>. We note, however, that the actual physics of magnetic dilution in CuGeO<sub>3</sub> is quite complex since dilution introduces frustration of the interchain elastic interaction . Replacement of Cu<sup>2+</sup> by Cd<sup>2+</sup> (Ref. ) or Ge<sup>4+</sup> by Ga<sup>4+</sup> (ref. ) both lead to mean field behavior over quite wide temperature ranges; that is, doping with these ions moves CuGeO<sub>3</sub> away from the tricritical point into the pure mean field regime. Again, further research, both experimental and theoretical, is required to elucidate these effects more completely.

## V Acknowledgements

We thank N. Hegman and J. C. Lasjaunias for comments on the manuscript, for sending us their results for $`C_M`$ in tabular form and for a preprint of Ref. . We are grateful to C. W. Garland and N. Goldenfeld for insightful communications on the interpretation of the critical heat capacity. We thank B. D. Gaulin for valuable comments on this paper and for drawing our attention to Ref. . This work was supported by the NSF under Grant No. DMR97-04532 and by the MRSEC Program of the NSF under award No. DMR98-08941.