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Journal of the Physical Society of Japan

A Semi-Phenomenological Theory of the Second Order Phase Transitions in Spin Systems. I

Masuo Suzuki

Published Mar 1, 1967• 8 citations
Publisher

Abstract

A semi-phenomenological theory is developed on the basis of some assumptions in order to study the singularities of thermodynamic quantities in the vicinity of the Curie point. First, microscopic expressions are found for the coefficients in the expansion of the thermodynamic potential in terms of cumulants. Cumulants of all order are calculated in the one-dimensional Ising model, and the series expansion of the fourth order cumulant is also obtained in the two-dimensional Ising model. The three-dimensional Heisenberg model is also discussed, using the result of Rushbrooke et al. In all cases, the fourth order coefficient in the expansion of the thermodynamic potential tends to zero at the Curie points. And, in the last case, the eighth order coefficient diverges at the Curie point.

DOI
10.1143/jpsj.22.757

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A semi-phenomenological theory is developed on the basis of some assumptions in order to study the singularities of thermodynamic quantities in the vicinity of the Curie point. First, microscopic expressions are found for the coefficients in the expansion of the thermodynamic potential in terms of cumulants. Cumulants of all order are calculated in the one-dimensional Ising model, and the series expansion of the fourth order cumulant is also obtained in the two-dimensional Ising model. The three-dimensional Heisenberg model is also discussed, using the result of Rushbrooke et al. In all cases, the fourth order coefficient in the expansion of the thermodynamic potential tends to zero at the Curie points. And, in the last case, the eighth order coefficient diverges at the Curie point.
To the lowest order approximation, the method of variational cumulant expansion has been successful in the determination of the critical point of a spin system on the Ising model. In the second order calculation, unphysical phase transition arises. In this letter, we first analyze the origin of unphysical phase transitions in high-order variational cumulant expansion calculations. We then explain the basis on which a conjecture is proposed that to any order m of the variational cumulant expansion, the critical point is given by the bifurcation point of the free energy. The theory is finally verified numerically for the two-dimensional case.
First, a new method proposed by Baker and Rushbrooke is used to study the simple ferromagnetic Ising model at and below the Curie temperature. Of course, the properties of the Ising model are already well known, so that the main aim here is to assess the potential and reliability of the new method, since it has wide applicability to other models which have not been otherwise studied. Between 8 and 16 coefficients of exact high-temperature expansions for fixed values of the magnetization are derived for various two- and three-dimensional lattices. A Pad\'e-approximant analysis of these expansions at the critical isotherm and magnetic phase boundary enables us to estimate the critical exponents $\ensuremath{\beta}$, ${\ensuremath{\gamma}}^{\ensuremath{'}}$, and $\ensuremath{\delta}$, and plot the spontaneous magnetization. The results are in good agreement with previous calculations. Secondly, an analysis of the exact series expansions provides no support for the conjecture that the phase boundary is a line of essential singularities. However, the same expansions strongly suggest the existence of a "spinodal" curve, whose properties are in reasonable agreement with the predictions of various heuristic arguments (based essentially upon analyticity at the phase boundary and one-phase homogeneity in the critical region). Finally, structure and a mild extension of the proven analyticity of the free energy are used to show the $\ensuremath{\Delta}\ensuremath{\le}{\ensuremath{\Delta}}^{\ensuremath{'}}$, $\ensuremath{\gamma}\ensuremath{\le}{\ensuremath{\gamma}}^{\ensuremath{'}}$.
The critical phenomenon of the second order phase transition is considered for temperatures above the critical point. A general phenomenological approach is developed. The generalized free energy F[{η q }: T ] is introduced. It is a functional of the Fourier component η q of the local order parameter η( r ). A general property of the correlation function <η q η - q > is established rigorously. The equilibrium free energy and the wave-number dependent susceptibility χ q are expressed in terms of the linked clusters, large clusters corresponding to highr order fluctuation of the order parameter. The general rule for calculating the contribution of each cluster is given. The rule is shown to be very simple. It is found that the specific heat is expressed as a sum of the temperature derivatives of χ q 's. As an example of the application of the linked cluster method, the susceptibility is calculated in the vicinity of the critical point by summing up the clusters that are most divergent when approaching the criticat point. The linked cluster expansion developed here could be a clue to the whole mystery of the singularity at the critical point.
Bose system of zero spin particles is considered in the presence of the Bose–Einstein condensate in the vicinity of the phase transition point. The system is investigated in the framework of the Bogolyubov model with the separated condensate. In this model an effective Hamiltonian of the system is introduced by replacing condensate creation and annihilation operators in system Hamiltonian by n01/2 where n0 is occupation number of the condensate state. According to Bogolyubov, the grand canonical thermodynamic potential related to the effective Hamiltonian is considered as nonequilibrium thermodynamic potential. In the present paper this potential is investigated as a function of the small variable n0. With the help of the thermodynamic perturbation theory it is shown that it is expanded in a series over integer powers of n0. This corresponds to the basic idea of the Landau theory of the phase transitions of the second kind. Coefficients at terms of the first and second orders in n0 in the expansion are calculated for Bose gas in the main approximation in small interaction. Calculation of the coefficients at terms of the third and fourth orders needs accounting contributions of the thermodynamic perturbation theory at least of the 4th order and will be done elsewhere. It is established that the results obtained for Bose gas do not fit into the Landau theory of phase transitions of the second kind. Some comments that discuss the situation are given.
The standard variational-cumulant expansion (VC) combined with a scheme for the enumeration of connected diagrams is employed to study the simple Ising model with the second-order phase transition. This model is evaluated to the 5th order approximations. A comparison with the 2-dimensional exact results shows that thermodynamic quantities converge rather slowly to the exact values in the intermediate region. A strict analytical calculation of the critical temperature with the 5th order approximation both for and cumulant expansion suggests that VC can achieve rather high standard accuracy if the variational parameters could be determined up to higher degrees of corrections rather than the first one. Anomalies are found for and at extremely low temperature. A detailed study of implies that thermodynamic formulae should be carefully chosen in VC approach so as to avoid these anomalies.