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Physical review. B, Condensed matter

Phase boundaries near critical end points. I. Thermodynamics and universality

Michael Ellis Fisher, Márcia C. Barbosa

Published May 1, 1991• 49 citations
Publisher

Abstract

The vicinity of a critical end point is analyzed in order to reveal singularities arising in the form of the first-order phase boundary to the noncritical phase. Phenomenological arguments are presented and critically assessed that directly relate the nonanalytic behavior of the phase boundary to universal features of the bulk thermodynamics on the associated critical line. Explicit values are given for universal amplitude ratios describing the boundary for various types of criticality.

DOI
10.1103/physrevb.43.11177

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A phenomenological description of first-order phase transitions is proposed in terms of the solution of a certain linear, first-order, partial differential equation suggested by Fisher. In the asymptotic region of the critical point, the coefficient functions of the equation are uniquely determined by the scaling laws. The imposition of the further requirement that the phase boundary coincide with a characteristic curve of this equation is shown to lead to solutions that can reproduce the singular behavior---for example, the density and entropy discontinuities for the case of the liquid-gas transition---along the entire vapor-pressure curve. The important role played by the characteristic curves is stressed and confirmed for the special case of the ideal, $d$-dimensional, Bose gas. New relations involving discontinuities in the second derivatives of the thermodynamic functions are derived and shown to be useful in obtaining the coefficient functions near the phase boundary. Details are presented for the case of ferromagnetic and ferroelectric systems and include a comparison with experiment.

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Critical phenomena in the bifurcation line's perspective

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On the phase diagram of a system undergoing a continuous phase transition of the second order, three lines, hyper-surfaces, convergent into the critical point feature prominently: the ordered and disordered phases in the thermodynamic limit, and a third line, extending into a domain of finite-size systems, defined by the bifurcation of the distribution of the order parameter. Unlike critical phenomena in the thermodynamic limit devoid of known thermodynamic potential and described rather by the conformal symmetry, in finite-size systems near the bifurcation line an explicit Hamiltonian for the zero-mode of the order parameter is found. It bears the impress of the universality class of the critical point in terms of the two critical exponents: $β$ and $ν$.

arXiv:1307.3826•Jul 15, 2013•0 citations
The vicinity of a critical end point is analyzed in order to reveal singularities arising in the form of the first-order phase boundary to the noncritical phase. Phenomenological arguments are presented and critically assessed that directly relate the nonanalytic behavior of the phase boundary to universal features of the bulk thermodynamics on the associated critical line. Explicit values are given for universal amplitude ratios describing the boundary for various types of criticality.
At a critical end point a critical phase coexists with a noncritical phase \ensuremath{\alpha} and singularities arise beyond those on the associated critical line. New universal amplitude ratios are defined for the shape of the \ensuremath{\alpha}-phase boundary and for the noncritical surface tensions near end points. A postulated correspondence with wall/surface criticality leads to predictions for general dimension d that are exact at (and near) d=2 and for d\ensuremath{\ge}4 (where mean-field theory applies) and yield experimentally testable estimates for d=3.
We study d-dimensional ferromagnetic spherical models with power-law, J(R)\ensuremath{\sim}1/${\mathit{R}}^{\mathit{d}+\mathrm{\ensuremath{\sigma}}}$ (\ensuremath{\sigma}2), or short-range (\ensuremath{\sigma}\ensuremath{\simeq}2) interactions and on-site terms of the form Ds2{\mathit{Ds}}^{2}Ds2-\ensuremath{\Vert}U\ensuremath{\Vert}s4{\mathit{s}}^{4}s4+Vs6{\mathit{Vs}}^{6}Vs6, and establish that the phase diagrams for all d and \ensuremath{\sigma} with \ensuremath{\sigma}d2\ensuremath{\sigma}, may exhibit critical end points terminating nonclassical critical lines; tricritical points may arise only for 3/2\ensuremath{\sigma}\ensuremath{\le}d. The phase boundary ${\mathit{D}}_{\mathrm{\ensuremath{\sigma}}}$(T,h), where h is the magnetic field, between the noncritical, spectator phase and the ordering and critical phase is shown to exhibit singularities at the end point with amplitudes obeying the universal ratio laws advanced on phenomenological grounds in Part I.
An introduction into the theory of boundary critical phenomena and the application of the field-theoretical renormalization group method to these is given. The emphasis is on a discussion of surface critical behavior at bulk critical points of magnets, binary alloys, and fluids. Yet a multitude of related phenomena are mentioned. The most important distinct surface universality classes that may occur for a given universality class of bulk critical behavior are described, and the respective boundary conditions of the associated field theories are discussed. The short-distance singularities of the order-parameter profile in the diverse asymptotic regimes are surveyed.
A phenomenological description of first-order phase transitions is proposed in terms of the solution of a certain linear, first-order, partial differential equation suggested by Fisher. In the asymptotic region of the critical point, the coefficient functions of the equation are uniquely determined by the scaling laws. The imposition of the further requirement that the phase boundary coincide with a characteristic curve of this equation is shown to lead to solutions that can reproduce the singular behavior---for example, the density and entropy discontinuities for the case of the liquid-gas transition---along the entire vapor-pressure curve. The important role played by the characteristic curves is stressed and confirmed for the special case of the ideal, ddd-dimensional, Bose gas. New relations involving discontinuities in the second derivatives of the thermodynamic functions are derived and shown to be useful in obtaining the coefficient functions near the phase boundary. Details are presented for the case of ferromagnetic and ferroelectric systems and include a comparison with experiment.
On the phase diagram of a system undergoing a continuous phase transition of the second order, three lines, hyper-surfaces, convergent into the critical point feature prominently: the ordered and disordered phases in the thermodynamic limit, and a third line, extending into a domain of finite-size systems, defined by the bifurcation of the distribution of the order parameter. Unlike critical phenomena in the thermodynamic limit devoid of known thermodynamic potential and described rather by the conformal symmetry, in finite-size systems near the bifurcation line an explicit Hamiltonian for the zero-mode of the order parameter is found. It bears the impress of the universality class of the critical point in terms of the two critical exponents: βββ and ννν.