In the present work, we discuss how the functional form of thermodynamic observables can be deduced from the geometric properties of subsets of phase space. The geometric quantities taken into account are mainly extrinsic curvatures of the energy level sets of the Hamiltonian of a system under investigation. In particular, it turns out that peculiar behaviours of thermodynamic observables at a phase transition point are rooted in more fundamental changes of the geometry of the energy level sets in phase space. More specifically, we discuss how microcanonical and geometrical descriptions of phase-transitions are shaped in the special case of $ϕ^4$ models with either nearest-neighbours and mean-field interactions.
In this paper, we consider the volume enclosed by the microcanonical ensemble in phase space as a statistical ensemble. This can be interpreted as an intermediate image between the microcanonical and the canonical pictures. By maintaining the ergodic hypothesis over this ensemble, that is, the equiprobability of all its accessible states, the equivalence of this ensemble in the thermodynamic limit with the microcanonical and the canonical ensembles is suggested by means of geometrical arguments. The Maxwellian and the Boltzmann-Gibbs distributions are obtained from this formalism. In the appen…
The microcanonical entropy $S=\ln[W(E)]$ is the {\em geometrical measure} of the microscopic redundancy or ignorance about the N-body system. {\em Even for astronomical large systems} is the microcanonical entropy everywhere {\em single valued and multiply differentiable}. Also the microcanonical temperature is at all energies single valued and differentiable. It is further shown that the recently introduced singularities of the {\em microcanonical} entropy like "microcanonical phase transitions", and exotic patterns of the {\em microcanonical} caloric curve $T(E)$ like multi-valuednes or the …
In the present work, we present a detailed discussion of a Riemannian metric structure originally introduced in [Gori et al., \textit{J. Stat. Mech.}, \textbf{9} 093204 (2018)] on the configuration space and on phase space allowing us to interpret the derivatives of the configurational microcanonical entropy and of the canonical entropy in terms of integrals of extrinsic geometrical quantities associated with the equipotential level sets.
We reconsider some general aspects about the mean field thermodynamical description of the astrophysical systems based on the microcanonical ensemble. Starting from these basis, we devote a special attention to the analysis of the scaling laws of the thermodynamical variables and potentials in the thermodynamic limit. Geometrical considerations motivate a way by means of which could be carried out a well-defined generalized canonical-like description for this kind of systems, even being nonextensive. This interesting possibility allows us to extend the applicability of the Standard Thermodynam…
More than a century has passed since van't Hoff and Arrhenius formulated their celebrated rate theories, but there are still elusive aspects in the temperature-dependent phase transition kinetics of molecular systems. Here I present a theory based on microcanonical thermostatistics that establishes a simple and direct temperature dependence for all rate constants, including the forward and the reverse rate constants, the equilibrium constant, and the nucleation rate. By considering a generic model that mimic the microcanonical temperature of molecular systems in a region close to a first-order…
Microcanonical thermostatistics analysis has become an important tool to reveal essential aspects of phase transitions in complex systems. An efficient way to estimate the microcanonical inverse temperature $β(E)$ and the microcanonical entropy $S(E)$ is achieved with the statistical temperature weighted histogram analysis method (ST-WHAM). The strength of this method lies on its flexibility, as it can be used to analyse data produced by algorithms with generalised sampling weights. However, for any sampling weight, ST-WHAM requires the calculation of derivatives of energy histograms $H(E)$, w…
Certain geometric properties of submanifolds of configuration space are numerically investigated for classical lattice phi^4 models in one and two dimensions. Peculiar behaviors of the computed geometric quantities are found only in the two-dimensional case, when a phase transition is present. The observed phenomenology strongly supports, though in an indirect way, a recently proposed topological conjecture about a topology change of the configuration space submanifolds as counterpart of a phase transition.
We discuss here the use of generalized forms of entropy, taken as information measures, to characterize phase transitions and critical behavior in thermodynamic systems. Our study is based on geometric considerations pertaining to the space of parameters that describe statistical mechanics models. The thermodynamic stability of the system is the focus of attention in this geometric context.
We discuss a geometrical interpretation of the Z-invariant Ising model in terms of isoradial embeddings of planar lattices. The Z-invariant Ising model can be defined on an arbitrary planar lattice if and only if certain paths on the lattice edges do not intersect each other more than once or self-intersect. This topological constraint is equivalent to the existence of isoradial embeddings of the lattice. Such embeddings are characterized by angles which can be related to the model coupling constants in the spirit of Baxter's geometrical solution. The Ising model on isoradial embeddings studie…
Critical exponent $γ\succeq 1.1$ characterizes behavior of the mechanical susceptibility of a real fluid when temperature approaches the critical one. It results in zero Gaussian curvature of the local shape of the critical point on the thermodynamic equation of state surface, which imposes a new constraint upon the construction of the potential equation of state of the real fluid from the empirical data. All known empirical equations of state suffer from a weakness that the Gaussian curvature of the critical point is negative definite instead of zero.
The thermodynamic properties of systems with long-range interactions is still an ongoing challenge, both from the point of view of theory as well as computer simulation. In this work we study a model system, a Coulomb gas confined inside a sphere, by using the Wang-Landau algorithm. We have computed the configurational density of states (CDOS), the thermodynamic entropy and the caloric curve, and compared with microcanonical Metropolis simulations, while showing how concepts such as the configurational inverse temperature can be used to understand some aspects of thermodynamic behavior. A dyna…
Recently, we have derived a generalization of the known canonical fluctuation relation $k_{B}C=β^{2}< δU^{2} >$ between heat capacity $C$ and energy fluctuations, which can account for the existence of macrostates with negative heat capacities $C<0$. In this work, we presented a panoramic overview of direct implications and connections of this fluctuation theorem with other developments of statistical mechanics, such as the extension of canonical Monte Carlo methods, the geometric formulations of fluctuation theory and the relevance of a geometric extension of the Gibbs canonical ensemble that…
We study a relationship between optimal transport theory and stochastic thermodynamics for the Fokker-Planck equation. We show that the lower bound on the entropy production is the action measured by the path length of the $L^2$-Wasserstein distance. Because the $L^2$-Wasserstein distance is a geometric measure of optimal transport theory, our result implies a geometric interpretation of the entropy production. Based on this interpretation, we obtain a thermodynamic trade-off relation between transition time and the entropy production. This thermodynamic trade-off relation is regarded as a the…
These lectures will address two questions. Is there a simple variational principle underlying the existence of secondary motifs in the native state of proteins? Is there a general approach which can qualitatively capture the salient features of the folding process and which may be useful for interpreting and guiding experiments? Here, we present three different approaches to the first question, which demonstrate the key role played by the topology of the native state of proteins. The second question pertaining to the folding dynamics of proteins remains a challenging problem -- a detailed desc…
We study the transport properties of continuous-time quantum walks (CTQW) over finite two-dimensional structures with a given number of randomly placed bonds and with different aspect ratios (AR). Here, we focus on the transport from, say, the left side to the right side of the structure where absorbing sites are placed. We do so by analyzing the long-time average of the survival probability of CTQW. We compare the results to the classical continuous-time random walk case (CTRW). For small AR (landscape configurations) we observe only small differences between the quantum and the classical tra…
We present a comprehensive study of non-equilibrium phenomena in the low temperature phase of the Edwards-Anderson Gaussian spin glass in 3 and 4 spatial dimensions. Many effects can be understood in terms of a time dependent coherence length, $\ell_T$, such that length scales smaller that $\ell_T$ are equilibrated, whereas larger length scales are essentially frozen. The time and temperature dependence of $\ell_T$ is found to be compatible with critical power-law dynamical scaling for small times/high temperatures, crossing over to an activated logarithmic growth for longer times/lower temper…
Motivated by the recent shocking results from RHIC and LHC that show quark-gluon plasma signatures in small systems, we study a simple model of a massless, noninteracting scalar field confined with Dirichlet boundary conditions. We use this system to investigate the finite size corrections to thermal field theoretically derived quantities compared to the usual Stefan-Boltzmann limit of an ideal gas not confined in any direction. Two equivalent expressions with different numerical convergence properties are found for the free energy in $D$ rectilinear spacetime dimensions with $c\le D-1$ spatia…
Equilibrium statistics of Hamiltonian systems is correctly described by the microcanonical ensemble. Classically this is the manifold of all points in the N-body phase space with the given total energy. Due to Boltzmann's principle, e^S=tr(δ(E-H)), its geometrical size is related to the entropy S(E,N,...). This definition does not invoke any information theory, no thermodynamic limit, no extensivity, and no homogeneity assumption, as are needed in conventional (canonical) thermo-statistics. Therefore, it describes the equilibrium statistics of extensive as well of non-extensive systems. Due to…
Equilibrium statistics of Hamiltonian systems is correctly described by the microcanonical ensemble. Classically this is the manifold of all points in the $N-$body phase space with the given total energy. Due to Boltzmann's principle, $e^S=tr(δ(E-H))$, its geometrical size is related to the entropy $S(E,N,...)$. This definition does not invoke any information theory, no thermodynamic limit, no extensivity, and no homogeneity assumption, as are needed in conventional (canonical) thermo-statistics. Therefore, it describes the equilibrium statistics of extensive as well of non-extensive systems. …
