# The effect of an external magnetic field on the gas-liquid transition in the Heisenberg spin fluid

## Abstract

We present the theoretical phase diagrams of the classical Heisenberg fluid in an external magnetic field. A consistent account of correlations is carried out by the integral equation method. A nonmonotoneous effect of fields on the temperature of the gas-liquid critical point is found. Within the mean spherical approximation this nonmonotoneous behavior disappears for short-range enough spin-spin interactions.

PACS numbers 61.20.Gy, 64.70.Fx, 75.50.Mm, 05.70.Jk.

The behavior of magnetic fluids in an external field compels more and more attention for the last years and has some peculiarities. In the presence of an external magnetic field the orientational (magnetic) phase transition is absent, but there are the first order transitions between ferromagnetic phases of different densities (e.g., gaseous and liquid phases). Physical properties of anisotropic fluids (to these belong also, besides magnetic fluids, nematic liquid crystals) are determined by the interplay between orientational and translational degrees of freedom. Therefore, varying the magnetic field it is possible to effect structural properties of magnetic fluids, in particular, to change the region of the gas-liquid coexistence. Such investigations with a calculation of phase diagrams were carried out for model spin systems within the mean field (MF) approximation . It was found that for fluids of hard spheres carrying Ising spins an external magnetic field decreases the temperature of the gas-liquid critical point. On the other hand, the presence of isotropic van der Waals attractions between molecules can lead to the inverse effect . In Ref.  the fluid of hard spheres with the classical Heisenberg spins and strong isotropic attractions was considered also. It was shown that at weak magnetic fields there can be two first order phase transitions in this model: gas-liquid and liquid-liquid. In strong fields the weak liquid-liquid transition disappears.

The need to account orientational-translational correlations for the description of physical properties of magnetic fluids stimulated studies of the external field effects by more complex techniques. The effect of an external field on the gas-liquid critical point was studied by the functional integration and Green function methods  for the quantum Heisenberg ferrofluid and by the Monte-Carlo and integral equation methods for the classical one . The pair potentials of those models consisted of contributions of hard spheres and of the spin-spin interaction (the so-called ideal Heisenberg fluid). In these works the conclusion was made that an external magnetic field favors the phase separation, i.e., the application of the external field increases the gas-liquid critical temperature. Let us note that the results of Refs.  are obtained for quite strong fields. In our point of view, it was the effect of small fields that is of special interest. This follows from the fact that at small fields orientational fluctuations are large and the corresponding correlations have a long-range character. Therefore, small external influences can result in significant changes of macroscopic properties of magnetic fluids. Besides, the interplay between orientational and spatial ordering can lead to an interesting behavior of the gas-liquid critical point at small fields. In this letter we show that in the systems with the long-range enough spin-spin interactions the nonmonotoneous effect of the external fields on the gas-liquid critical temperature takes place. There is a temperature range, where weak external fields suppress the gas-liquid phase separation. By the integral equation method we show that while the range parameter of the model potential decreases this temperature interval first gets smaller and then disappears.

We shall consider the model that was studied before for the case of zero external field . The pair potential (analogically to the papers ) is a sum of the hard sphere potential $`\phi (R_{12})`$ for spheres of diameter $`\sigma `$ and of the Heisenberg spin-spin potential $`\mathrm{\Phi }(R_{12},\omega _1,\omega _2)`$

$`\mathrm{\Phi }(R_{12},\omega _1,\omega _2)=J(R_{12})\widehat{𝑺}_1\widehat{𝑺}_2,`$ (1)   
$`J(R)=K{\displaystyle \frac{(z\sigma )^2}{z\sigma +1}}{\displaystyle \frac{\mathrm{exp}(z(R\sigma ))}{R/\sigma }},`$ (2)   
where $`\widehat{𝑺}_i`$ is a unit vector in the direction $`\omega _i=(\theta _i,\phi _i)`$ of the magnetic dipole moment $`𝝁`$, referred to the uniform field $`B_0`$ as the $`z`$ direction. The potential of the particle interacting with the field is $`v_i=\mu B_0\mathrm{cos}\theta _i`$. In expression (2) the coefficient $`\frac{(z\sigma )^2}{z\sigma +1}`$ is chosen to make the integral

$$I=\frac{N^2}{2V}𝑑\omega _1𝑑\omega _2\underset{R_{12}>\sigma }{}𝑑𝑹_{12}\mathrm{\Phi }(R_{12},\omega _1,\omega _2)f(\omega _1)f(\omega _2)$$
(3)   
(where $`f(\omega )`$ is a single-particle orientational distribution function) independent of $`z\sigma `$. The integral $`I`$ describes a contribution of the spin-spin potential into the free energy functional within the MF approximation (see, for example, ). Therefore, within the MF approach the model phase diagram is independent of $`z\sigma `$, if we use dimensionless units for the temperature $`t=k_\mathrm{B}T/K`$, the density $`\eta =\frac{N}{V}\frac{\pi \sigma ^3}{6}`$, and the external field strength $`h=\frac{\mu B_0}{K\sqrt{3}}`$. For the free energy of the hard sphere system we use the “quasi-exact” Carnahan-Starling expression . The MF phase diagrams obtained by the well-known double-tangent construction are presented in Fig. 1. One can see a nonmonotoneous effect of the external field on the temperature of the gas-liquid critical point at small values of $`h`$. With the increase of the external field strength the gas-liquid critical point first moves down ($`h=0.1`$, 0.5), then moves up ($`h=2`$, 5), and last ($`h=10`$, 20, $`\mathrm{}`$) grows higher than the top of the zero field binodal. It should be noted that the model potential (2) in the limit $`z\sigma 0`$ belongs to a family of the so-called Kac potentials, for which the MF approach is accurate. Therefore, relying on the MF results (Fig. 1) we can state that for long-range enough spin-spin interactions ($`z\sigma 0`$) the nonmonotoneous field effect on the critical temperature does take place. But for finite values of $`z\sigma `$ we are forced to carry out more accurate investigation.

More consistent consideration of anisotropic fluids can be done on the basis of the integral equation method that allows to calculate both the one-particle distribution function and the pair distribution function. The task consists  in a solution of the anisotropic Ornstein-Zernike (OZ) equation

$$h(1,2)=c(1,2)+\rho (3)h(1,3)c(3,2)d(3),$$
(4)   
where $`d(3)=d𝑹_3d\omega _3`$, $`\rho (1)=\rho f(\omega _1)`$, $`h(1,2)`$ and $`c(1,2)`$ are the total and direct correlation functions of the system. Since Eq. (4) contains the one-particle distribution function, we need (besides a closure relation for the anisotropic OZ equation) some additional relation for determination of $`\rho (1)`$. It can be the first equation of the Bogolubov-Born-Green-Kirkwood-Yvon hierarchy (this was used in Refs.  to obtain a numerical solution of Eq. (4)) or the Lovett equation for anisotropic fluids 

$$\mathbf{}_{\omega _1}\mathrm{ln}\rho (1)+\mathbf{}_{\omega _1}\frac{v(1)}{k_\mathrm{B}T}=c(1,2)\mathbf{}_{\omega _2}\rho (2)d(2),$$
(5)   
where $`\mathbf{}_{\omega _1}`$ is an angular gradient operator; $`v(1)`$ is a potential of interaction with a uniform external field, its spherical harmonic expansion is of the form

$$v(1)=\underset{l}{}v_lY_{l0}(\omega _1).$$
(6)   
For a self-consistent solution of Eqs. (4) and (5) we shall use the method suggested in . The method is based on the algebraic representation of the Lovett equation for uniaxial fluids. Using the general expansion for the direct correlation function of linear molecules

$$c(1,2)=\underset{\genfrac{}{}{0pt}{}{mnl}{\mu \nu \lambda }}{}c_{mnl}^{\mu \nu \lambda }(R)Y_{m\mu }(\omega _1)Y_{n\nu }^{}(\omega _2)Y_{l\lambda }(\omega _R)$$
(7)   
and the exponential form of the one-particle distribution function

$$f(\omega )=Z^1\mathrm{exp}\left(\underset{l>0}{}A_lY_{l0}(\omega )\right)$$
(8)   
we obtain following  an algebraic representation of the Lovett equation for a uniaxial fluid in the external field

$$L_l=\underset{mn}{}C_{lm}Y_{mn}L_n+V_l=\underset{m}{}C_{lm}𝒫_m+V_l,$$
(9)   
where all indices take the values greater or equal one, $`V_l=v_l/k_\mathrm{B}T`$, $`C_{mn}=c_{mn0}^{110}(R)𝑑𝑹`$, $`Y_{mn}=\rho Y_{m1}(\omega )Y_{n1}^{}(\omega )_\omega `$, $`\mathrm{}_\omega =f(\omega )(\mathrm{})𝑑\omega `$, $`L_l=\sqrt{l(l+1)}A_l`$, $`𝒫_l=\rho \sqrt{l(l+1)(2l+1)}P_l(\mathrm{cos}\theta )_\omega `$, $`P_l(\mathrm{cos}\theta )`$ is the $`l`$th order Legendre polynomial. Let us note that the average values $`P_l(\mathrm{cos}\theta )_\omega `$ play the role of order parameters in anisotropic fluids. Relations (9) are accurate, and their use, as well as the use of the integro-differential equation (5), does not introduce any approximation into the theory.

Due to (9) it turns to be possible to obtain for the model (1)–(2) an analytical solution of the anisotropic OZ equation (4) within the mean spherical closure

$$\begin{array}{cc}c(1,2)=\mathrm{\Phi }(R_{12},\omega _1,\omega _2)/k_\mathrm{B}T,\hfill & R_{12}>\sigma ,\hfill \\ h(1,2)=1,\hfill & R_{12}<\sigma .\hfill \end{array}$$
(10)   
Condition (10) for $`h(1,2)`$ follows directly from the fact that hard spheres do not overlap. The mean spherical closure (10) restricts correlation functions of our model to those of the form

$$f(1,2)=\underset{l_1l_2m}{}f_{l_1l_2m}(R_{12})Y_{l_1m}(\omega _1)Y_{l_2m}^{}(\omega _2),$$
(11)   
($`l_1,l_2=0,1`$), and representation (9) results in equalities

$`A_1`$ $`=`$ $`A_1\rho \left|Y_{11}(\omega )\right|^2_\omega {\displaystyle c_{111}(R)𝑑𝑹}+{\displaystyle \frac{v_1}{k_\mathrm{B}T}},`$ (12)   
$`A_1`$ $`=`$ $`A_1\rho Y_{10}(\omega )_\omega {\displaystyle c_{111}(R)𝑑𝑹}+{\displaystyle \frac{v_1}{k_\mathrm{B}T}}.`$ (13)   
Here we use the notations of Eq. (11) for harmonics of the direct correlation function $`c(1,2)`$; $`v_1=\mu B_0/\sqrt{3}`$. Thus, the use of the mean spherical closure yields for our model vanishing of coefficients $`A_l`$ with $`l>1`$ in Eq. (8), and the self-consistent one-particle distribution function in the mean spherical approximation (MSA) takes the form

$$f(\omega )=\mathrm{exp}\left(A_1Y_{10}(\omega )\right)/\mathrm{exp}\left(A_1Y_{10}(\omega )\right)𝑑\omega .$$
(14)   
A uniaxial symmetry of our system leads to factorization of Eq. (4) on the equations with different $`m`$. At $`m=\pm 1`$

$`h_{11m}(R_{12})`$ $`=`$ $`c_{11m}(R_{12})`$ (15)   
$`+`$ $`\rho \left|Y_{1m}(\omega )\right|^2_\omega {\displaystyle c_{11m}(R_{13})h_{11m}(R_{32})𝑑𝑹_3}.`$ (16)   
For $`m=0`$ we have a system of integral equations that after the Fourier transformation gains the matrix form

$$H_{ij}(k)=C_{ij}(k)+\underset{i^{}j^{}}{}C_{ii^{}}(k)\rho _{i^{}j^{}}H_{j^{}j}(k),$$
(17)   
where $`H_{ij}(k)=h_{ij0}(k)`$, $`C_{ij}(k)=c_{ij0}(k)`$, $`\rho _{ij}=\rho Y_{i0}(\omega )Y_{j0}(\omega )_\omega `$, indices take the values 0 and 1. The problem of a self-consistent solution of the anisotropic OZ and Lovett equations has reduced at this stage to the solution of Eqs. (15) and (17) under conditions (13) and the self-consistent $`f(\omega )`$ given by relation (14). On the basis of the Wertheim-Baxter factorization method  one can find the analytical solution of such equations in the form of a set of algebraic equations. The detailed derivation of similar solutions can be found in the literature, and therefore we omit any details and refer the reader to the previous publications . The explicit form of the solution is quite unwieldy and will be given in the extended version of this paper. Here we point out only that it is efficiently computable, and we use it for calculation of isotherms by the virial route to thermodynamics in order to locate the gas-liquid transition by the Maxwell construction.

The configuration of the MSA zero-field phase diagrams slightly differs from that of the MF theory (Fig. 1). The MSA via the virial route to thermodynamics demonstrates (Fig. 2) the lack of the tricritical point  in the Heisenberg fluid (1)–(2) contrary to the MF and modified MF theories . Within the MSA the Curie line joins the gas-liquid binodal at its vapor branch (see insets to Fig. 2). This result is in whole agreement with the available zero-field simulations for the same model : the liquid phase is ferromagnetic and the gaseous phase is mainly paramagnetic, except in the neighborhood of the critical point, where the transition ferroliquid-ferrogas takes place. The quantitative agreement with simulations is also quite perfect (see Fig. 2a). In the insets to the figure one can distinguish the critical point (CP, the top of the gas-liquid binodal) and the critical endpoint (CEP) in which the Curie line joins the binodal. In the temperature range from $`t_{\mathrm{CEP}}`$ to $`t_{\mathrm{CP}}`$ three spatially uniform phases (isotropic gas, ferrogas, ferroliquid) can exist. For long-range enough potentials this interval ($`t_{\mathrm{CP}}t_{\mathrm{CEP}}`$) decreases with the decrease of $`z\sigma `$ (see table I) and tends to zero for small values of $`z\sigma `$: the CP and the CEP coincide and form the tricritical point as is shown in Fig. 1. In practice we can not distinguish the CP and the CEP by the MSA virial route already at $`z\sigma =0.1`$.

The effect of strong magnetic fields on the Heisenberg fluid (1)–(2) consists in a considerable increase of the critical temperature. Strong external fields spread the gas-liquid coexistence region on the phase diagram, in other words, favors the gas-liquid phase separation. This result agrees with the conclusions of Refs. . But it follows from the MSA phase diagrams in Fig. 2 that small fields can suppress the gas-liquid transition at finite values of $`z\sigma `$ (not only in the limit $`z\sigma 0`$). For example, one can see on Fig. 2a ($`z\sigma =1`$) that the external field of strength $`h=0.1`$ totally removes the phase separation at temperatures from $`t_{\mathrm{CP}}(0.1)=1.002`$ to $`t_{\mathrm{CP}}(0)=1.043`$. In the systems with more short-range anisotropic interactions this temperature interval decreases. For example, in Fig. 2b ($`z\sigma =2`$) the temperature interval, where the external field $`h=0.1`$ removes the gas-liquid separation, is much less. For short-range enough potentials even very weak fields do not suppress separation, e.g., for $`z\sigma =3`$ the same field $`h=0.1`$ increases $`t_{\mathrm{CP}}`$ (Fig. 2c). Thus, the MSA predicts that the suppression effect of small fields on the gas-liquid separation gets weak and finally disappears for short-range enough spin-spin interactions. The verification of this conclusion we address to future investigations.

Acknowledgements. We are grateful to I. M. Mryglod for he compelled our attention to the problem. We thank J. J. Weis for sending us Ref.  prior to publication. We also thank H. Iro and R. Folk for giving us the paper Ref.  prior to publication and for useful discussion.