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Register a new userGibbs and Boltzmann Entropy in Classical and Quantum Mechanics
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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.
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In a recent paper, Dunkel and Hilbert [Nature Physics 10, 67-72 (2014)] use an entropy definition due to Gibbs to provide a consistent thermostatistics which forbids negative absolute temperatures. Here we argue that the Gibbs entropy fails to satisfy a basic requirement of thermodynamics, namely that when two bodies are in thermal equilibrium, they should be at the same temperature. The entropy definition due to Boltzmann does meet this test, and moreover in the thermodynamic limit can be shown to satisfy Dunkel and Hilberts consistency criterion. Thus, far from being forbidden, negative temperatures are inevitable, in systems with bounded energy spectra.
Boltzmanns ergodic hypothesis furnishes a possible explanation for the emergence of statistical mechanics in the framework of classical physics. In quantum mechanics, the Eigenstate Thermalization Hypothesis (ETH) is instead generally considered as a possible route to thermalization. This is because the notion of ergodicity itself is vague in the quantum world and it is often simply taken as a synonym for thermalization. Here we show, in an elementary way, that when quantum ergodicity is properly defined, it is, in fact, equivalent to ETH. In turn, ergodicity is equivalent to thermalization, thus implying the equivalence of thermalization and ETH. This result previously appeared in [De Palma et al., Phys. Rev. Lett. 115, 220401 (2015)], but becomes particularly clear in the present context. We also show that it is possible to define a classical analogue of ETH which is implicitly assumed to be satisfied when constructing classical statistical mechanics. Classical and quantum statistical mechanics are built according to the familiar standard prescription. This prescription, however, is ontologically justified only in the quantum world.
We generalize the convex duality symmetry in Gibbs statistical ensemble formulation, between Massieus free entropy $Phi_{V,N} (beta)$ and the Gibbs entropy $varphi_{V,N}(u)$ as a function of mean internal energy $u$. The duality tells us that Gibbs thermodynamic entropy is to the law of large numbers (LLN) for arithmetic sample means what Shannons information entropy is to the LLN for empirical counting frequencies. Following the same logic, we identify $u$ as the conjugate variable to counting frequency, a Hamilton-Jacobi equation for Shannon entropy as an equation of state, and suggest an eigenvalue problem for modeling statistical frequencies of correlated data.
This paper introduces the basic concepts of information theory. Based on these concepts, we regard the states in the state space and the types of ideal gases as the symbols in a symbol set to calculate the mixing entropy of ideal gas involved in Gibbs Paradox. The discussion above reveals that the non-need for distinguishing can resolve the contradiction of Gibbs Paradox, implying the introduction of indistinguishability is not necessary. Further analysis shows that the information entropy of gas molecular types does not directly correlate to the energy of a gas system, so it should not be used for calculating thermodynamic and statistical dynamic entropies. Therefore, the mixing entropy of the ideal gas is independent of the molecular types and is much smaller than the value commonly thought.
We develop the framework of classical Observational entropy, which is a mathematically rigorous and precise framework for non-equilibrium thermodynamics, explicitly defined in terms of a set of observables. Observational entropy can be seen as a generalization of Boltzmann entropy to systems with indeterminate initial conditions, and describes the knowledge achievable about the system by a macroscopic observer with limited measurement capabilities; it becomes Gibbs entropy in the limit of perfectly fine-grained measurements. This quantity, while previously mentioned in the literature, has been investigated in detail only in the quantum case. We describe this framework reasonably pedagogically, then show that in this framework, certain choices of coarse-graining lead to an entropy that is well-defined out of equilibrium, additive on independent systems, and that grows towards thermodynamic entropy as the system reaches equilibrium, even for systems that are genuinely isolated. Choosing certain macroscopic regions, this dynamical thermodynamic entropy measures how close these regions are to thermal equilibrium. We also show that in the given formalism, the correspondence between classical entropy (defined on classical phase space) and quantum entropy (defined on Hilbert space) becomes surprisingly direct and transparent, while manifesting differences stemming from non-commutativity of coarse-grainings and from non-existence of a direct classical analogue of quantum energy eigenstates.
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