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arXiv:1511.06176

Quantum Thermodynamics, Entropy of the Universe, Free Energy, and the Second Law

George L. Barnes, Phillip C. Lotshaw, Michael E. Kellman

Published Nov 19, 2015• 1 citation
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Abstract

We take the view that the standard von Neumann definition, in which the entropy $S^{vN}$ of a pure state is zero, is in evident conflict with the statement of the second law that the entropy of the universe $S_{univ}$ increases in spontaneous processes, $ ΔS_{univ} > 0$. Here we seek an alternative entropy of the universe $S_{univ}$ that is in accord with the second law, in a spirit not dissimilar to von Neumann himself in lesser-known work. We perform simulations of time dependent dynamics for a previously developed \cite{polyadbath} model quantum system becoming entangled with a quantum environment. We test the new definition of the entropy of the system-environment "universe" against the standard thermodynamic relation $ ΔF_{sys} = - T ΔS_{univ} $, calculating system properties using the reduced density matrix and standard von Neumann entropy. Good agreement is obtained, showing the compatibility of an entropy for a pure state of a universe with the statement of the second law and the concept of free energy. Interesting deviation from microcanonical behavior within the zero order energy shell is observed in a context of effectively microcanonical behavior within the much larger total basis of the time dependent universe.

DOI
10.48550/arxiv.1511.06176

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We take the view that the standard von Neumann definition, in which the entropy SvNS^{vN}SvN of a pure state is zero, is in evident conflict with the statement of the second law that the entropy of the universe SunivS_{univ}Suniv​ increases in spontaneous processes, ΔSuniv>0 ΔS_{univ} > 0ΔSuniv​>0. Here we seek an alternative entropy of the universe SunivS_{univ}Suniv​ that is in accord with the second law, in a spirit not dissimilar to von Neumann himself in lesser-known work. We perform simulations of time dependent dynamics for a previously developed \cite{polyadbath} model quantum system becoming entangled with a quantum environment. We test the new definition of the entropy of the system-environment "universe" against the standard thermodynamic relation ΔFsys=−TΔSunivΔF_{sys} = - T ΔS_{univ}ΔFsys​=−TΔSuniv​, calculating system properties using the reduced density matrix and standard von Neumann entropy. Good agreement is obtained, showing the compatibility of an entropy for a pure state of a universe with the statement of the second law and the concept of free energy. Interesting deviation from microcanonical behavior within the zero order energy shell is observed in a context of effectively microcanonical behavior within the much larger total basis of the time dependent universe.
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We explore a recently introduced quantum thermodynamic entropy SunivQS^Q_{univ}SunivQ​ of a pure state of a composite system-environment computational "universe" with a simple system S\mathcal{S}S coupled to a constant temperature bath E\mathcal{E}E. The principal focus is "excess entropy production" in which the quantum entropy change is greater than expected from the classical entropy-free energy relationship. We analyze this in terms of quantum spreading of time dependent states, and its interplay with the idea of a microcanonical shell. The entropy takes a basis-dependent Shannon information definition. We argue for the zero-order SE\mathcal{SE}SE energy basis as the unique choice that gives classical thermodynamic relations in the limit of weak coupling and high density of states, including an exact division into system and environment components. Entropy production takes place due to two kinds of processes. The first is classical "ergodization" that fills the full density of states within the microcanonical shell. The second is excess entropy production related to quantum spreading or "quantum ergodization" of the wavepacket that effectively increases the width of the energy shell. Lorentzian superpositions with finite microcanonical shell width lead to classical results as the limiting case, with no excess entropy. We then consider a single SE\mathcal{SE}SE zero-order initial state, as the examplar of extreme excess entropy production. Systematic formal results are obtained for a unified treatment of excess entropy production for time-dependent Lorentzian superpositions, and verified computationally. It is speculated that the idea of free energy might be extended to a notion of "available energy" corresponding to the excess entropy production. A unified perspective on quantum thermodynamic entropy is thereby attained from the classical limit to extreme quantum conditions.
Recent theoretical and experimental work on the foundations of statistical mechanics and thermodynamics has shown that quantum pure states typically evolve to thermal equilibrium. We focus on formulating the second law of thermodynamics for these states. The standard quantum von Neumann quantum entropy is constant during equilibration, S^{vN}=0, in apparent conflict with the entropy increase of the second law, ΔS_{univ} > 0. We explore a recently developed entropy S_{univ}^Q for a pure state and test its behavior in simulations of a model system and environment evolving in time with heat flow to equilibrium. We find that the entropy approaches the correct classical value in a type of classical limit with weak coupling. With stronger coupling, we find a new source of quantum "excess entropy production," which has its origin in the quantum spreading of the wavepacket. Are there quantum thermodynamic effects related to this new source of entropy? To test this, we developed a model for a small variable temperature quantum oscillator bath. We performed simulations where two small baths are linked by a system, with unequal couplings to the baths. The model evolves to a novel type of equilibrium state with unequal temperatures in the baths, with heat flow from cold to hot along the path to equilibrium. We give an account of this behavior in terms of the second law with the quantum entropy S_{univ}^Q. The new formulation of the second law thus appears well-founded and fruitful, with surprising new quantum thermodynamic effects that may still be awaiting discovery, for example in molecules or systems far from equilibrium. \n\nThis dissertation includes previously published and unpublished co-authored material.
For a quantum state undergoing unitary Schrodinger time evolution, the von Neumann entropy is constant. Yet the second law of thermodynamics, and our experience, show that entropy increases with time. Ingarden introduced the quantum operator entropy, which is the Shannon entropy of the probability distribution for the eigenvalues of a Hermitian operator. These entropies characterize the missing information about a particular observable inherent in the quantum state itself. The von Neumann entropy is the quantum operator entropy for the case when the operator is the density matrix. We examine pure state unitary evolution in a simple model system comprised of a set of highly-interconnected topologically disordered states and a time-independent Hamiltonian. An initially confined state is subject to free expansion into available states. The time development is completely reversible with no loss of quantum information and no course graining is applied. The positional entropy increases in time in a way that is consistent with both the classical statistical mechanical entropy and the second law.
A central open question in quantum thermodynamics is the identification of thermodynamic entropy away from equilibrium. Although thermodynamic entropy coincides with the von Neumann entropy for a Gibbs state at equilibrium, the thermodynamic role of quantum coherence generated during nonequilibrium evolution remains unclear. Here, we show that von Neumann entropy does not, in general, represent the thermodynamic entropy governing heat exchange in coherent nonequilibrium quantum systems. By integrating the resource theory of quantum coherence with thermodynamic principles, we develop a general framework for nonequilibrium quantum thermodynamics. We identify thermodynamic entropy with the energy entropy derived from energy-measurement statistics and introduce a dynamical temperature extending the equilibrium concept to nonequilibrium states. Consequently, we obtain an exact entropy-balance relation separating the entropy flux associated with heat exchange from the coherence-loss contribution to entropy production, establishing an operational connection between quantum coherence, heat flow, and total entropy change. Unlike approaches relying on equilibrium reference states or stationary Gibbs ensembles, our framework uses instantaneous dynamical quantities and remains valid throughout transient nonequilibrium evolution. It provides consistent dynamical definitions of temperature, work, heat, and free energy. Applying the formalism to an exactly solvable open quantum system, we show that the first and second laws hold throughout transient evolution and that equilibrium thermodynamics emerges dynamically in the weak-coupling long-time limit. Our results establish a unified framework for coherent nonequilibrium quantum thermodynamics and suggest opportunities for controlling heat dissipation through coherence engineering in quantum thermal technologies.
For a quantum state undergoing unitary Schrödinger time evolution, the von Neumann entropy is constant. Yet the second law of thermodynamics, and our experience, show that entropy increases with time. Ingarden introduced the quantum operator entropy, which is the Shannon entropy of the probability distribution for the eigenvalues of a Hermitian operator [R. S. Ingarden, Quantum information theory, Rep. Math. Phys. 10, 43 (1976)RMHPBE0034-487710.1016/0034-4877(76)90005-7]. These entropies characterize the missing information about a particular observable inherent in the quantum state itself. The von Neumann entropy is the quantum operator entropy for the case when the operator is the density matrix. We examine pure state unitary evolution in a simple model system composed of a set of highly interconnected topologically disordered states and a time-independent Hamiltonian. An initially confined state is subject to free expansion into available states. The time development is completely reversible with no loss of quantum information and no course graining is applied. The positional entropy increases in time in a way that is consistent with both the classical statistical mechanical entropy and the second law.