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Do negative absolute temperatures matter physics and specifically Statistical Physics? We provide evidence that we can certainly answer positively to this vexata quaestio. The great majority of models investigated by statistical mechanics over almost one century and a half exhibit positive absolute temperature, because their entropy is a nondecreasing function of energy. Since more than half a century ago it has been realized that this may not be the case for some physical systems as incompressible fluids, nuclear magnetic chains, lasers, cold atoms and optical waveguides. We review these examples and discuss their peculiar thermodynamic properties, which have been associated to the presence of thermodynamic regimes, characterized by negative absolute temperatures. As reported in this review, the ambiguity inherent the definition of entropy has recurrently raised a harsh debate about the possibility of considering negative temperature states as genuine thermodynamic equilibrium ones. Here we show that negative absolute temperatures are consistent with equilibrium as well as with non-equilibrium thermodynamics. In particular, thermometry, thermodynamics of cyclic transformations, ensemble equivalence, fluctuation-dissipation relations, response theory and even transport processes can be reformulated to include them, thus dissipating any prejudice about their exceptionality, typically presumed as a manifestation of transient metastable effects.
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The statistical mechanics of periodically driven (Floquet) systems in contact with a heat bath exhibits some radical differences from the traditional statistical mechanics of undriven systems. In Floquet systems all quasienergies can be placed in a finite frequency interval, and the number of near degeneracies in this interval grows without limit as the dimension N of the Hilbert space increases. This leads to pathologies, including drastic changes in the Floquet states, as N increases. In earlier work these difficulties were put aside by fixing N, while taking the coupling to the bath to be smaller than any quasienergy difference. This led to a simple explicit theory for the reduced density matrix, but with some major differences from the usual time independent statistical mechanics. We show that, for weak but finite coupling between system and heat bath, the accuracy of a calculation within the truncated Hilbert space spanned by the N lowest energy eigenstates of the undriven system is limited, as N increases indefinitely, only by the usual neglect of bath memory effects within the Born and Markov approximations. As we seek higher accuracy by increasing N, we inevitably encounter quasienergy differences smaller than the system-bath coupling. We therefore derive the steady state reduced density matrix without restriction on the size of quasienergy splittings. In general, it is no longer diagonal in the Floquet states. We analyze, in particular, the behavior near a weakly avoided crossing, where quasienergy near degeneracies routinely appear. The explicit form of our results for the denisty matrix gives a consistent prescription for the statistical mechanics for many periodically driven systems with N infinite, in spite of the Floquet state pathologies.
Recently, we have presented some simple arguments supporting the existence of certain complementarity between thermodynamic quantities of temperature and energy, an idea suggested by Bohr and Heinsenberg in the early days of Quantum Mechanics. Such a complementarity is expressed as the impossibility of perform an exact simultaneous determination of the system energy and temperature by using an experimental procedure based on the thermal equilibrium with other system regarded as a measure apparatus (thermometer). In this work, we provide a simple generalization of this latter approach with the consideration of a thermodynamic situation with several control parameters.
The local equilibrium approach previously developed by the Authors [J. Mabillard and P. Gaspard, J. Stat. Mech. (2020) 103203] for matter with broken symmetries is applied to crystalline solids. The macroscopic hydrodynamics of crystals and their local thermodynamic and transport properties are deduced from the microscopic Hamiltonian dynamics. In particular, the Green-Kubo formulas are obtained for all the transport coefficients. The eight hydrodynamic modes and their dispersion relation are studied for general and cubic crystals. In the same twenty crystallographic classes as those compatible with piezoelectricity, cross effects coupling transport between linear momentum and heat or crystalline order are shown to split the degeneracy of damping rates for modes propagating in opposite generic directions.
We address the statistical mechanics of randomly and permanently crosslinked networks. We develop a theoretical framework (vulcanization theory) which can be used to systematically analyze the correlation between the statistical properties of random networks and their histories of formation. Generalizing the original idea of Deam and Edwards, we consider an instantaneous crosslinking process, where all crosslinkers (modeled as Gaussian springs) are introduced randomly at once in an equilibrium liquid state, referred to as the preparation state. The probability that two functional sites are crosslinked by a spring exponentially decreases with their distance squared. After formally averaging over network connectivity, we obtained an effective theory with all degrees of freedom replicated 1 + n times. Two thermodynamic ensembles, the preparation ensemble and the measurement ensemble, naturally appear in this theory. The former describes the thermodynamic fluctuations in the state of preparation, while the latter describes the thermodynamic fluctuations in the state of measurement. We classify various correlation functions and discuss their physical significances. In particular, the memory correlation functions characterize how the properties of networks depend on their history of formation, and are the hallmark properties of all randomly crosslinked materials. We clarify the essential difference between our approach and that of Deam-Edwards, discuss the saddle-point order parameters and its physical significance. Finally we also discuss the connection between saddle-point approximation of vulcanization theory, and the classical theory of rubber elasticity as well as the neo-classical theory of nematic elastomers.
We provide here an explicit example of Khinchins idea that the validity of equilibrium statistical mechanics in high dimensional systems does not depend on the details of the dynamics. This point of view is supported by extensive numerical simulation of the one-dimensional Toda chain, an integrable non-linear Hamiltonian system where all Lyapunov exponents are zero by definition. We study the relaxation to equilibrium starting from very atypical initial conditions and focusing on energy equipartion among Fourier modes, as done in the original Fermi-Pasta-Ulam-Tsingou numerical experiment. We find evidence that in the general case, i.e., not in the perturbative regime where Toda and Fourier modes are close to each other, there is a fast reaching of thermal equilibrium in terms of a single temperature. We also find that equilibrium fluctuations, in particular the behaviour of specific heat as function of temperature, are in agreement with analytic predictions drawn from the ordinary Gibbs ensemble, still having no conflict with the established validity of the Generalized Gibbs Ensemble for the Toda model. Our results suggest thus that even an integrable Hamiltonian system reaches thermalization on the constant energy hypersurface, provided that the considered observables do not strongly depend on one or few of the conserved quantities. This suggests that dynamical chaos is irrelevant for thermalization in the large-$N$ limit, where any macroscopic observable reads of as a collective variable with respect to the coordinate which diagonalize the Hamiltonian. The possibility for our results to be relevant for the problem of thermalization in generic quantum systems, i.e., non-integrable ones, is commented at the end.
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