Abstract In this paper we explore the following question: can the probabilities constituting the quantum Boltzmann distribution, , be derived from a requirement that the quantum configuration-space distribution for a system in thermal equilibrium be very similar to the corresponding classical distribution? It is certainly to be expected that the quantum distribution in configuration space will approach the classical distribution as the temperature approaches infinity, and a well-known equation derived from the Boltzmann distribution shows that this is generically the case. Here we ask whether one can reason in the opposite direction, that is, from quantum-classical agreement to the Boltzmann probabilities. For two of the simple examples we consider—a particle in a 1D box and a simple harmonic oscillator—this approach leads to probability distributions that provably approach the Boltzmann probabilities at high temperature, in the sense that the Kullback–Leibler divergence between the distributions approaches zero.
Abstract In this paper we explore the following question: can the probabilities constituting the quantum Boltzmann distribution, , be derived from a requirement that the quantum configuration-space distribution for a system in thermal equilibrium be very similar to the corresponding classical distribution? It is certainly to be expected that the quantum distribution in configuration space will approach the classical distribution as the temperature approaches infinity, and a well-known equation derived from the Boltzmann distribution shows that this is generically the case. Here we ask whether one can reason in the opposite direction, that is, from quantum-classical agreement to the Boltzmann probabilities. For two of the simple examples we consider—a particle in a 1D box and a simple harmonic oscillator—this approach leads to probability distributions that provably approach the Boltzmann probabilities at high temperature, in the sense that the Kullback–Leibler divergence between the distributions approaches zero.
Abstract In this chapter, we continue our parallel exploration of statistical and computational physics, but now move to the field of quantum mechanics, where the density matrix generalizes the classical Boltzmann distribution. The density matrix constructs the quantum statistical probabilities from their two origins: the quantum mechanical wave functions and the Boltzmann probabilities of the energy levels. The density matrix can thus be defined in terms of the complete solution of the quantum problem (wave functions, energies), but all this information is available only in simple examples, such as the free particle or the harmonic oscillator. A simple general expression exists for the density matrix only at high temperature.
It is pointed out that the quantum-mechanical Boltzmann H theorem in the restricted sense (i.e. with explicit consideration of the statistics of the particles constituting the system and their interactions) does not lead directly to the distribution laws for the particles among their various states as is commonly believed, but to the equality of the probability for all states belonging to the system as a whole if the system is isolated, (or to the Boltzmann factor for the probabilities of states belonging to a system at constant temperature), in agreement with the result of the generalized quantum-mechanical H theorem as given by Pauli. The distribution laws for the particles among their various states may of course be deduced from the latter.In the course of proof, we have also introduced the following minor improvements:(i) To avoid conservation of energy in microscopic processes which lead to changes in the states of the particles and thus to equilibrium, we let our system be in interaction with a heat reservoir, so that energy may be supplied by or given to it. This is tauto-mount to changing the study of the entropy for an isolated system to that of the free energy for a system at constant temperature.(ii) Interaction energies between the particles which affect the total energy of the system and thus the distribution laws for the particles among their various states are included.
The Gibbs entropy of a macroscopic classical system is a function of a probability distribution over phase space, i.e., of an ensemble. In contrast, the Boltzmann entropy is a function on phase space, and is thus defined for an individual system. Our aim is to discuss and compare these two notions of entropy, along with the associated ensemblist and individualist views of thermal equilibrium. Using the Gibbsian ensembles for the computation of the Gibbs entropy, the two notions yield the same (leading order) values for the entropy of a macroscopic system in thermal equilibrium. The two approaches do not, however, necessarily agree for non-equilibrium systems. For those, we argue that the Boltzmann entropy is the one that corresponds to thermodynamic entropy, in particular in connection with the second law of thermodynamics. Moreover, we describe the quantum analog of the Boltzmann entropy, and we argue that the individualist (Boltzmannian) concept of equilibrium is supported by the recent works on thermalization of closed quantum systems.
The Gibbs entropy of a macroscopic classical system is a function of a probability distribution over phase space, i.e., of an ensemble. In contrast, the Boltzmann entropy is a function on phase space, and is thus defined for an individual system. Our aim is to discuss and compare these two notions of entropy, along with the associated ensemblist and individualist views of thermal equilibrium. Using the Gibbsian ensembles for the computation of the Gibbs entropy, the two notions yield the same (leading order) values for the entropy of a macroscopic system in thermal equilibrium. The two approaches do not, however, necessarily agree for non-equilibrium systems. For those, we argue that the Boltzmann entropy is the one that corresponds to thermodynamic entropy, in particular, in connection with the second law of thermodynamics. Moreover, we describe the quantum analog of the Boltzmann entropy, and we argue that the individualist (Boltzmannian) concept of equilibrium is supported by the recent works on thermalization of closed quantum systems.
Abstract. It is demonstrated that the statistical mechanical partition function can be used to construct various different forms of phase space distributions. This indicates that its structure is not restricted to the Gibbs–Boltzmann factor prescription which is based on counting statistics. With the widely used replacement of the Boltzmann factor by a generalised Lorentzian (also known as the q-deformed exponential function, where κ = 1∕|q − 1|, with κ, q ∈ R) both the kappa-Bose and kappa-Fermi partition functions are obtained in quite a straightforward way, from which the conventional Bose and Fermi distributions follow for κ → ∞. For κ ≠ ∞ these are subject to the restrictions that they can be used only at temperatures far from zero. They thus, as shown earlier, have little value for quantum physics. This is reasonable, because physical κ systems imply strong correlations which are absent at zero temperature where apart from stochastics all dynamical interactions are frozen. In the classical large temperature limit one obtains physically reasonable κ distributions which depend on energy respectively momentum as well as on chemical potential. Looking for other functional dependencies, we examine Bessel functions whether they can be used for obtaining valid distributions. Again and for the same reason, no Fermi and Bose distributions exist in the low temperature limit. However, a classical Bessel–Boltzmann distribution can be constructed which is a Bessel-modified Lorentzian distribution. Whether it makes any physical sense remains an open question. This is not investigated here. The choice of Bessel functions is motivated solely by their convergence properties and not by reference to any physical demands. This result suggests that the Gibbs–Boltzmann partition function is fundamental not only to Gibbs–Boltzmann but also to a large class of generalised Lorentzian distributions as well as to the corresponding nonextensive statistical mechanics.
In this paper we suggest a simple mathematical procedure to derive the classical probability density of quantum systems via Bohr’s correspondence principle. Using Fourier expansions for the classical and quantum distributions, we assume that the Fourier coefficients coincide for the case of large quantum number. We illustrate the procedure by analyzing the classical limit for the quantum harmonic oscillator and the particle in a box, although the method is quite general. We find, in an analytical fashion, the classical distribution arising from the quantum one as the zeroth order term in an expansion in powers of Planck’s constant. We interpret the correction terms as residual quantum effects at the microscopic-macroscopic boundary.