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arXiv:1010.2646 · Journal of the Physical Society of Japan

Approach to Equilibrium in Nano-scale Systems at Finite Temperature

Fengping Jin, Hans A. De Raedt, Shengjun Yuan, Mikhail I. Katsnelson, Seiji Miyashita, Kristel F. L. Michielsen

Published Dec 10, 2010• 30 citations
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Abstract

We study the time evolution of the reduced density matrix of a system of spin-1/2 particles interacting with an environment of spin-1/2 particles.The initial state of the composite system is taken to be a product state of a pure state of the system and a pure state of the environment.The latter pure state is prepared such that it represents the environment at a given finite temperature in the canonical ensemble.The state of the composite system evolves according to the time-dependent Schrödinger equation, the interaction creating entanglement between the system and the environment.It is shown that independent of the strength of the interaction and the initial temperature of the environment, all the eigenvalues of the reduced density matrix converge to their stationary values, implying that also the entropy of the system relaxes to a stationary value.We demonstrate that the difference between the canonical density matrix and the reduced density matrix in the stationary state increases as the initial temperature of the environment decreases.As our numerical simulations are necessarily restricted to a modest number of spin-1/2 particles (< 36), but do not rely on time-averaging of observables nor on the assumption that the coupling between system and environment is weak, they suggest that the stationary state of the system directly follows from the time evolution of a pure state of the composite system, even if the size of the latter cannot be regarded as being close to the thermodynamic limit.

DOI
10.1143/jpsj.79.124005

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We study the time evolution of the reduced density matrix of a system of spin-1/2 particles interacting with an environment of spin-1/2 particles.The initial state of the composite system is taken to be a product state of a pure state of the system and a pure state of the environment.The latter pure state is prepared such that it represents the environment at a given finite temperature in the canonical ensemble.The state of the composite system evolves according to the time-dependent Schrödinger equation, the interaction creating entanglement between the system and the environment.It is shown that independent of the strength of the interaction and the initial temperature of the environment, all the eigenvalues of the reduced density matrix converge to their stationary values, implying that also the entropy of the system relaxes to a stationary value.We demonstrate that the difference between the canonical density matrix and the reduced density matrix in the stationary state increases as the initial temperature of the environment decreases.As our numerical simulations are necessarily restricted to a modest number of spin-1/2 particles (< 36), but do not rely on time-averaging of observables nor on the assumption that the coupling between system and environment is weak, they suggest that the stationary state of the system directly follows from the time evolution of a pure state of the composite system, even if the size of the latter cannot be regarded as being close to the thermodynamic limit.
In this review, we discuss the decoherence and thermalization of a quantum spin system interacting with a spin bath environment, by numerically solving the time-dependent Schrödinger equation of the whole system. The effects of the topologic structure and the initial state of the environment on the decoherence of the two-spin and many-spin system are discussed. The role of different spin-spin coupling is considered. We show under which conditions the environment drives the reduced density matrix of the system to a fully decoherent state, and how the diagonal elements of the reduced density matrix approach those expected for the system in the microcanonical or canonical ensemble, depending on the character of the additional integrals of motion. Our demonstration does not rely on time-averaging of observables nor does it assume that the coupling between system and bath is weak. Our findings show that the microcanonical distribution (in each eigenenergy subspace) and canonical ensemble are states that may result from pure quantum dynamics, suggesting that quantum mechanics may be regarded as the foundation of quantum statistical mechanics. Furthermore, our numerical results show that a fully decoherent quantum system prefers to stay in an equilibrium state with a maximum entropy, indicating the validity of the second law of thermodynamics in the decoherence process.
A system composed of identical spins and described by a quantum mechanical pure state is analyzed within the statistical framework presented in Part I of this work. We explicitly derive the typical values of the entropy, of the energy, and of the equilibrium reduced density matrix of a subsystem for the two different statistics introduced in Part I. In order to analyze their consistency with thermodynamics, these quantities of interest are evaluated in the limit of large number of components of the isolated system. The main results can be summarized as follows: typical values of the entropy and of the equilibrium reduced density matrix as functions of the internal energy in the fixed expectation energy ensemble do not satisfy the requirement of thermodynamics. On the contrary, the thermodynamical description is recovered from the random pure state ensemble (RPSE), provided that one considers systems large enough. The thermodynamic limit of the considered properties for the spin system reveals a number of important features. First canonical statistics (and thus, canonical typicality as long as the fluctuations around the average value are small) emerges without the need of assuming the microcanonical space for the global pure state. Moreover, we rigorously prove (i) the equivalence of the "global temperature," derived from the entropy equation of state, with the "local temperature" determining the canonical state of the subsystems; and (ii) the equivalence between the RPSE typical entropy and the canonical entropy for the overall system.
We solve the time-dependent Schrodinger equation for the combination of a spin system interacting with a spin bath environment. In particular, we focus on the time development of the reduced density matrix of the spin system. Under normal circumstances we show that the environment drives the reduced density matrix to a fully decoherent state, and furthermore the diagonal elements of the reduced density matrix approach those expected for the system in the canonical ensemble. We show one exception to the normal case is if the spin system cannot exchange energy with the spin bath. Our demonstration does not rely on time-averaging of observables nor does it assume that the coupling between system and bath is weak. Our findings show that the canonical ensemble is a state that may result from pure quantum dynamics, suggesting that quantum mechanics may be regarded as the foundation of quantum statistical mechanics.
By numerically exact calculations of spin-1/2 antiferromagnetic Heisenberg models on small clusters up to 24 sites, we demonstrate that quantum entanglement between subsystems A and B in a pure ground state of a whole system A + B can induce thermal equilibrium in subsystem A. Here, the whole system is bipartitoned with the entanglement cut that covers the entire volume of subsystem A. An effective temperature T A of subsystem A induced by quantum entanglement is not a parameter but can be determined from the entanglement von Neumann entropy S A and the total energy E A of subsystem A calculated for the ground state of the whole system.We show that temperature T A can be derived by minimizing the relative entropy for the reduced density matrix operator of subsystem A and the Gibbs state (i.e., thermodynamic density matrix operator) of subsystem A with respect to the coupling strength between subsystems A and B. Temperature T A is essentially identical to the thermodynamic temperature, for which the entropy and the internal energy evaluated using the canonical ensemble in statistical mechanics for the isolated subsystem A agree numerically with the entanglement entropy S A and the total energy E A of subsystem A. Fidelity calculations ascertain that the reduced density matrix operator of subsystem A for the pure but entangled ground state of the whole system A + B matches, within a maximally 1.5% error in the finite size clusters studied, the thermodynamic density matrix operator of subsystem A at temperature T A , despite that these density-matrix operators are different in general.We also find that temperature T A evaluated from the ground state of the whole system depends insignificantly on the system sizes, which is consistent with the fact that the thermodynamic temperature is an intensive quantity.We argue that quantum fluctuation in an entangled pure state can mimic thermal fluctuation in a subsystem.We also provide two simple but nontrivial analytical examples of free bosons and free fermions for which the two density-matrix operators are exactly the same if the effective temperature T A is adopted.We furthermore discuss implications and possible applications of our finding.
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.
Simulations are performed of a small quantum system interacting with a quantum environment. The system consists of various initial states of two harmonic oscillators coupled to give normal modes. The environment is "designed" by its level pattern to have a thermodynamic temperature. A random coupling causes the system and environment to become entangled in the course of time evolution. The approach to a Boltzmann distribution is observed, and effective fitted temperatures close to the designed temperature are obtained. All initial pure states of the system are driven to equilibrium at very similar rates, with quick loss of memory of the initial state. The time evolution of the von Neumann entropy is calculated as a measure of equilibration and of quantum coherence. It is pointed out using spatial density distribution plots that quantum interference is eliminated only with maximal entropy, which corresponds thermally to infinite temperature. Implications of our results for the notion of "classicalizing" behavior in the approach to thermal equilibrium are briefly considered.