The paper analyzes the probability distribution of the occupancy numbers and the entropy of a system at the equilibrium composed by an arbitrary number of non-interacting bosons. The probability distribution is obtained through two approaches: one involves tracing out the environment from a bosonic eigenstate of the combined environment and system of interest (the empirical approach), while the other involves tracing out the environment from the mixed state of the combined environment and system of interest (the Bayesian approach). In the thermodynamic limit, the two coincide and are equal to the multinomial distribution. Furthermore, the paper proposes to identify the physical entropy of the bosonic system with the Shannon entropy of the occupancy numbers, fixing certain contradictions that arise in the classical analysis of thermodynamic entropy. Finally, by leveraging an information-theoretic inequality between the entropy of the multinomial distribution and the entropy of the multivariate hypergeometric distribution, Bayesianism of information theory and empiricism of statistical mechanics are integrated into a common "infomechanical" framework.
The paper analyzes the probability distribution of the occupancy numbers and the entropy of a system at the equilibrium composed by an arbitrary number of non-interacting bosons. The probability distribution is obtained through two approaches: one involves tracing out the environment from a bosonic eigenstate of the combined environment and system of interest (the empirical approach), while the other involves tracing out the environment from the mixed state of the combined environment and system of interest (the Bayesian approach). In the thermodynamic limit, the two coincide and are equal to the multinomial distribution. Furthermore, the paper proposes to identify the physical entropy of the bosonic system with the Shannon entropy of the occupancy numbers, fixing certain contradictions that arise in the classical analysis of thermodynamic entropy. Finally, by leveraging an information-theoretic inequality between the entropy of the multinomial distribution and the entropy of the multivariate hypergeometric distribution, Bayesianism of information theory and empiricism of statistical mechanics are integrated into a common "infomechanical" framework.
In this work, we compare three formulations of thermodynamic entropy for a non-interacting bosonic gas: (i) the grand-canonical Bose-Einstein entropy, (ii) the finite-N canonical entropy obtained from the exact partition function (Ziff, Uhlenbeck, and Kac construction), and (iii) the entropy of a multinomial distribution with Boltzmann categorical probabilities and temperature determined from Clausius' equation. It is well-known that the grand-canonical Bose-Einstein systematically overestimates entropy of canonical systems in regimes where particle-number fluctuations are significant. The exact canonical entropy correctly enforces the particle-number constraint, but recent experimental results suggest that it also overestimates particle-number fluctuations below the crossover temperature. The multinomial distribution is less common in thermodynamics. It addresses in a mathematically exact way the puzzle of the famous -log(N!) term introduced by Gibbs as a deus ex machina in discussions of thermodynamic entropy. One remarkable consequence is that the entropy of the multinomial distribution overcomes the issue of negative entropy at low temperature that affects the Gibbs and the Sackur-Tetrode entropies at low temperature. The analysis presented in the paper shows that the multinomial distribution, equipped with a categorical distribution calibrated in such a way that the resulting multinomial entropy fits Clausius' equation, provides accurate approximations to the canonical entropy in the classical regime, while it is smaller than the canonical entropy below the crossover temperature. One feature of the multinomial distribution is that it predicts lower peak variance of the number of particles in the ground state than the canonical distribution. This is in agreement with recent experimental results; hence, this paper identifies the thermodynamically calibrated multinomial distribution as a candidate alternative to the canonical distribution for thermodynamic bosonic entropy in finite systems.
The paper analyzes the entropy of a system composed by non-interacting and indistinguishable particles whose quantum state numbers are modelled as independent and identically distributed classical random variables. The crucial observation is that, under this assumption, whichever is the number of particles that constitute the system, the occupancy numbers of system's quantum (micro)states are multinomially distributed. This observation leads to an entropy formula for the physical system, which is nothing else than the entropy formula of the multinomial distribution, for which we claim novelty, in the sense that it is proposed here for the first time that the entropy of the multinomial distribution is the entropy of the physical system. The entropy formula of the multinomial distribution unveils yet unexplored connections between information theory and statistical mechanics, among which we mention the connection between conditional entropy of the random microstate given the random occupancy numbers and the Boltzmann-Planck entropy log(W) and between these two and the Gibbs correction term log(N!), thermalization and communication-theoretic preparation of a thermal state, accessible information of the thermal state and physical entropy of the thermalized system. A noticeable specific result that descends from our approach is the exact quantum correction to the textbook Sackur-Tetrode formula for the entropy of an ideal gas at the thermal equilibrium in a container.
The paper works out the canonical probability distribution of the occupancy numbers of a bosonic system and shows that canonical typicality applies to the canonical density operator of the occupancy numbers. The result is that, if, as it is today standard, the canonical system's mixed state is obtained by tracing out the environment from any typical pure state of the universe, then asymptotically the canonical probability distribution of system's occupancy numbers tends in probability to the multinomial distribution. The paper also shows that the currently accepted probability distribution of the occupancy numbers of a system with fixed number of particles is not compatible with the commonly accepted notion of canonical system.
This paper introduces a novel definition of non-classical information entropy, rooted in the principles of statistical physics, particularly quantum mechanics. The core premise is that traditional information entropy, derived from classical probability theory, is insufficient to capture the essence of information within non-classical systems exhibiting phenomena such as superposition and entanglement. We propose a definition based on the concept of accessible states and their associated probabilities, extending the notion of entropy beyond the realm of purely deterministic systems. The paper details the mathematical formulation of this non-classical information entropy, denoted as *Hnc*, and presents a method for its calculation. The method relies on identifying the set of accessible states for a given system and then applying a generalized form of Shannon's entropy formula, modified to account for the inherent uncertainties associated with quantum mechanics. The resulting *Hnc* provides a quantitative measure of the information content within non-classical systems, offering a potential framework for studying information processing and dynamics in quantum environments. The key contribution lies in bridging the gap between information theory and non-classical statistical physics, offering a new lens through which to understand information in quantum systems.
A probability distribution encodes all the statistics of its corresponding random variable, hence it encodes all one can learn about the system via the random variable. In the theoretical part of this thesis, we discuss several equivalent representations of probability distributions in physics which establishes their roles as complete information measures in their own contexts. In particular, we show how Rényi entropies (as well as relative Rényi entropies) completely characterise the uncertainty of a system, hence implies the insufficiency of Shannon entropy (as well as relative entropy) in capturing the information in the presence of strong fluctuation. We also generalise Jarzynski equality in terms of relative Rényi entropies and show the equivalence between the generalised equality and the work distribution. As a consequence, an equivalence between a monotonic property of relative Rényi entropies and a kind of second law relations is revealed. In the experimental part, we study the non-equilibrium dynamics of an optically levitated nanosphere system in Knudsen regime and discover that, even though the system is not in equilibrium, the dynamics can still be treated as a Brownian motion with an effective temperature and an effective coefficient. Due to the Gaussian statistics of the levitated sphere, we show how some relevant non-equilibrium properties of the system, including several local temperatures, can be analysed from its power spectrum.
Descriptions of molecular systems usually refer to two distinct theoretical frameworks. On the one hand the quantum pure state, i.e., the wavefunction, of an isolated system is determined to calculate molecular properties and their time evolution according to the unitary Schrödinger equation. On the other hand a mixed state, i.e., a statistical density matrix, is the standard formalism to account for thermal equilibrium, as postulated in the microcanonical quantum statistics. In the present paper an alternative treatment relying on a statistical analysis of the possible wavefunctions of an isolated system is presented. In analogy with the classical ergodic theory, the time evolution of the wavefunction determines the probability distribution in the phase space pertaining to an isolated system. However, this alone cannot account for a well defined thermodynamical description of the system in the macroscopic limit, unless a suitable probability distribution for the quantum constants of motion is introduced. We present a workable formalism assuring the emergence of typical values of thermodynamic functions, such as the internal energy and the entropy, in the large size limit of the system. This allows the identification of macroscopic properties independently of the specific realization of the quantum state. A description of material systems in agreement with equilibrium thermodynamics is then derived without constraints on the physical constituents and interactions of the system. Furthermore, the canonical statistics is recovered in all generality for the reduced density matrix of a subsystem.