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It is widely believed that the underlying reality behind statistical mechanics is a deterministic and unitary time evolution of a many-particle wave function, even though this is in conflict with the irreversible, stochastic nature of…
The foundations of the Boltzmann-Gibbs (BG) distributions for describing equilibrium statistical mechanics of systems are examined. Broadly, they fall into: (i) probabilistic paaroaches based on the principle of equal a priori probability…
Traditionally, phase transitions are defined in the thermodynamic limit only. We propose a new formulation of equilibrium thermo-dynamics that is based entirely on mechanics and reflects just the {\em geometry and topology} of the N-body…
The entropy of a classical thermally isolated Hamiltonian system is given by the logarithm of the measure of phase space enclosed by the constant energy hyper-surface, also known as volume entropy. It has been shown that on average the…
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,…
We present a scheme to evaluate thermodynamic variables for a system coupled to a heat bath under a time-dependent external force using the quasi-static Helmholtz energy from the numerically "exact" hierarchical equations of motion (HEOM).…
We consider an isolated system in an arbitrary state and provide a general formulation using first principles for an additive and non-negative statistical quantity that is shown to reproduce the equilibrium thermodynamic entropy of the…
The Boltzmann-Gibbs celebrated entropy $S_{BG}=-k\sum_ip_i \ln p_i$ is {\it concave} (with regard to all probability distributions $\{p_i\}$) and {\it stable} (under arbitrarily small deformations of any given probability distribution). It…
There is a well-known analogy between statistical and quantum mechanics. In statistical mechanics, Boltzmann realized that the probability for a system in thermal equilibrium to occupy a given state is proportional to exp(-E/kT) where E is…
The basic notions of statistical mechanics (microstates, multiplicities) are quite simple, but understanding how the second law arises from these ideas requires working with cumbersomely large numbers. To avoid getting bogged down in…
The microscopic explanation of entropy has been challenged from both experimental and theoretical point of view. The expression of entropy is derived from the first law of thermodynamics indicating that entropy or the second law of…
A pedagogical derivation of statistical mechanics from quantum mechanics is provided, by means of open quantum systems. Besides, a new definition of Boltzmann entropy for a quantum closed system is also given to count microstates in a way…
The problem of temperature in nonextensive statistical mechanics is studied. Considering the first law of thermodynamics and a "quasi-reversible process", it is shown that the Tsallis entropy becomes the Clausius entropy if the inverse of…
Boltzmann's principle is used to select the "most probable" realization (macrostate) of an isolated or closed thermodynamic system, containing a small number of particles ($N \llsp \infty$), for both classical and quantum statistics. The…
The entropy of a thermally isolated system should not decrease after a quench or external driving. For a classical system following Hamiltonian dynamics, we show how this statement emerges for a large system in the sense that the extensive…
Boltzmann's principle S(E,N,V...)=ln W(E,N,V...) allows the interpretation of Statistical Mechanics of a closed system as Pseudo-Riemannian geometry in the space of the conserved parameters E,N,V... (the conserved mechanical parameters in…
Conventional thermo-statistics address infinite homogeneous systems within the canonical ensemble. However, some 170 years ago the original motivation of thermodynamics was the description of steam engines, i.e. boiling water. Its essential…
We generalize the usual exponential Boltzmann factor to any reasonable and potentially observable distribution function, $B(E)$. By defining generalized logarithms $\Lambda$ as inverses of these distribution functions, we are led to a…
According to Boltzmann-Gibbs (BG) statistical mechanics, the thermodynamic response, such as the isothermal susceptibility, at critical points (CPs) presents a divergent-like behavior. An appropriate parameter to probe both classical and…
We revisit the controversy, discussed recently by Goldstein in this journal[J. Chem. Phys. 128,154510 (2008)], whether the residual entropy is real or fictional. It is shown that the residual entropy loss conjecture (ELC) at the glass…