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Phase Transitions

Microcanonical analysis of small systems

Michel Pleimling, H. Behringer

Published Sep 1, 2005• 18 citations
Publisher

Abstract

The basic quantity for the description of the statistical properties of physical systems is the density of states or, equivalently, the microcanonical entropy. Macroscopic quantities of a system in equilibrium can be computed directly from the entropy. Response functions such as the susceptibility are related, for example, to the curvature of the entropy surface. Interestingly, physical quantities in the microcanonical ensemble show characteristic properties of phase transitions in finite systems. In this article we investigate these characteristics for finite Ising systems. The singularities in microcanonical quantities, which signal a continuous phase transition in infinite systems, are characterized by classical critical exponents. Estimates of the non-classical exponents which emerge only in the thermodynamic limit can nevertheless be obtained by analysing effective exponents or by applying a microcanonical finite-size scaling theory. This is explicitly demonstrated for two- and three-dimensional Ising systems.

DOI
10.1080/01411590500288999

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The basic quantity for the description of the statistical properties of physical systems is the density of states or, equivalently, the microcanonical entropy. Macroscopic quantities of a system in equilibrium can be computed directly from the entropy. Response functions such as the susceptibility are related, for example, to the curvature of the entropy surface. Interestingly, physical quantities in the microcanonical ensemble show characteristic properties of phase transitions in finite systems. In this article we investigate these characteristics for finite Ising systems. The singularities in microcanonical quantities, which signal a continuous phase transition in infinite systems, are characterized by classical critical exponents. Estimates of the non-classical exponents which emerge only in the thermodynamic limit can nevertheless be obtained by analysing effective exponents or by applying a microcanonical finite-size scaling theory. This is explicitly demonstrated for two- and three-dimensional Ising systems.
The basic quantity for the description of the statistical properties of physical systems is the density of states or equivalently the microcanonical entropy. Macroscopic quantities of a system in equilibrium can be computed directly from the entropy. Response functions such as the susceptibility are for example related to the curvature of the entropy surface. Interestingly, physical quantities in the microcanonical ensemble show characteristic properties of phase transitions already in finite systems. In this paper we investigate these characteristics for finite Ising systems. The singularities in microcanonical quantities which announce a continuous phase transition in the infinite system are characterised by classical critical exponents. Estimates of the non-classical exponents which emerge only in the thermodynamic limit can nevertheless be obtained by analyzing effective exponents or by applying a microcanonical finite-size scaling theory. This is explicitly demonstrated for two- and three-dimensional Ising systems.
Physical quantities obtained from the microcanonical entropy surfaces of classical spin systems show typical features of phase transitions already in finite systems. It is demonstrated that the singular behaviour of the microcanonically defined order parameter and susceptibility can be understood from a Taylor expansion of the entropy surface. The general form of the expansion is determined from the symmetry properties of the microcanonical entropy function with respect to the order parameter. The general findings are investigated for the four-state vector Potts model as an example of a classical spin system.
The properties of an infinite system at a continuous phase transition are characterised by non-trivial critical exponents. These non-trivial exponents are related to scaling relations of the thermodynamic potential. The scaling properties of the singular part of the specific entropy of infinite systems are deduced starting from the well-established scaling relations of the Gibbs free energy. Moreover, it turns out that the corrections to scaling are suppressed in the microcanonical ensemble compared to the corresponding corrections in the canonical ensemble.
For models which exhibit a continuous phase transition in the thermodynamic limit a numerical study of small systems reveals a non-monotonic behaviour of the microcanonical specific heat as a function of the system size. This is in contrast to a treatment in the canonical ensemble where the maximum of the specific heat increases monotonically with the size of the system. A phenomenological theory is developed which permits us to describe this peculiar behaviour of the microcanonical specific heat and allows in principle the determination of microcanonical critical exponents.
Due to the equivalence of the statistical ensembles, thermostatic properties of physical systems with short-range interactions can be calculated in different ensembles leading to the same physics. In particular, the ensemble equivalence holds for systems that undergo a continuous phase transition in the infinite volume limit with the result that the properties of the transition can also be investigated in the microcanonical approach. Considering as an example the spherical model, the ensemble equivalence is explicitly demonstrated by calculating the critical properties in the microcanonical ensemble and comparing them to the well known canonical results.
Phase transitions are conventionally defined by nonanalyticities of thermodynamic potentials in the thermodynamic limit. In this Letter, we show that the singularity is not the definition of criticality but its asymptotic outcome: criticality is already written in the microcanonical entropy derivatives at any finite size as intrinsic morphological structures -- inflection points and extrema. The singularity is then the endpoint of a sharpening process that evolves with increasing system size. Combining microcanonical inflection-point analysis (MIPA) with the Berlin-Kac spherical model -- for which the microcanonical density of states is known in closed form at every finite NNN -- we systematically identify these structures in the energy profiles of entropy derivatives that encode the transition. An inflection point in the inverse temperature βN(ε)=∂εSNβ_N(ε)=\partial_εS_NβN​(ε)=∂ε​SN​ and a pronounced peak in its derivative γN(ε)=∂ε2SNγ_N(ε)=\partial^2_εS_NγN​(ε)=∂ε2​SN​ define a well-controlled pseudocritical trajectory whose controlled sharpening and drift culminate in the macroscopic cusp at the critical energy εcε_cεc​ in the thermodynamic limit. This establishes an intrinsic, order-parameter-free notion of criticality that precedes its singular asymptotic representation.