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Proceedings of the National Academy of Sciences

A general treatment of relaxation phenomena

S. H. Lin, Henry B. Eyring

Published Sep 1, 1977• 43 citations
Publisher

Abstract

The singular perturbation method has been applied to solve the quantum mechanical Liouville equation for the relaxation phenomenon of the system in thermal contact with a heat bath. The master equation derived gives the proper expressions for both diagonal and off-diagonal elements of the density matrix and is capable of describing the time-dependent behavior of the system in the time range comparable with the reciprocal of the damping constants and the time range t --> infinity compared with the reciprocal of the damping constants.

DOI
10.1073/pnas.74.9.3623

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The singular perturbation method has been applied to solve the quantum mechanical Liouville equation for the relaxation phenomenon of the system in thermal contact with a heat bath. The master equation derived gives the proper expressions for both diagonal and off-diagonal elements of the density matrix and is capable of describing the time-dependent behavior of the system in the time range comparable with the reciprocal of the damping constants and the time range t --> infinity compared with the reciprocal of the damping constants.
A general procedure is given for finding the equation of motion of the density matrix of a system in contact with a thermal bath, as for example a nuclear spin system weakly coupled to a crystal lattice. The thermal bath is treated both classically and quantum mechanically, and the theory is similar to, and a generalization of, conventional theories of time proportional transition probabilities. Relaxation of the system by the thermal bath is expressed by a linear matrix operator, and it is stressed that elements of this operator can be regarded as secular or nonsecular perturbations on the equation of motion and can be treated accordingly. When the motion of the system is slow compared to that of the thermal bath, the equation of motion can be expressed in an operator form which is independent of representation. If the system has a time-dependent Hamiltonian which varies slowly compared to the motion of the thermal bath, the same equation of motion is obeyed and the system is relaxed by the bath toward a Boltzmann distribution with respect to its instantaneous Hamiltonian. If the time variation of the Hamiltonian is more rapid, higher order corrections to the equation of motion must be applied. The theory is applied to spin-lattice relaxation of a coupled nuclear spin system in a metal, for arbitrary externally applied fixed magnetic field.
For pt.I see ibid. vol.16, p.3987-4000, (1983). The determinantal formalism for solving the time-dependent Schrodinger equation of the density matrix has been developed, in I, assuming a constant external perturbation. The important case of an harmonic perturbation is presented here. Detailed expressions are derived for diagonal and nondiagonal elements of the response, and the trace conservation theorem is shown to be satisfied at all times and any order. The results are again applied to the simple illustrative quantum system considered in I.
A time-convolutionless expression for the quantal equation of motion for the linear response of a system in contact with a heat bath to an external, time-varying driving field is derived from the quantal Liouville equation of motion for the total system. This is done by renormalizing the memory effect by the method of Shibata, Takahashi and Hashitsume. It has a form convenient for the perturbational expansion. It is shown that this equation coincides with the time-convolution equation of Argyres and Kelley in their Markoffian approximation in the narrowing limit and in the lowest Born approximation for the system-bath interaction. This equation is expanded up to fourth order in powers of the system-bath interaction.
Using the exact path integral solution for the damped harmonic oscillator it is shown that in general there does not exist an exact dissipative Liouville operator describing the dynamics of the oscillator for arbitrary initial bath preparations. Exact nonstationary Liouville operators can be found only for particular preparations. Three physically meaningful examples are examined. An exact master equation is derived for thermal initial conditions. Second, the Liouville operator governing the time evolution of equilibrium correlations is obtained. Third, factorizing initial conditions are studied. Additionally, one can show that there are approximate Liouville operators independent of the initial preparation describing the long-time dynamics under appropriate conditions. The general form of these approximate master equations is derived and the coefficients are determined for special cases of the bath spectral density including the Ohmic, Drude, and weak coupling cases. The connection with earlier work is discussed.
This is the second in a series of papers which intends to develop a statistical mechanical theory capable of independently treating responses to thermal as well as mechanical disturbances. The essential idea is to develop a method of solving the Liouvill-von Neumann equation for the density matrix of a many-body system in a time-dependent Gibbsian form. The theory is made determinate by defining the relative entropy, which will reflect the character of the entropy production in our model. In this paper, rigorous expressions are obtained for nonlinear responses, which contain all the most general consequences of statistical mechanics regarding the macroscopic variables. In particular, the Onsager reciprocity relations follow from the formula in nonlinear regions. An attempt to treat a stationary state where heat is produced is made in terms of a nonequilibrium density matrix satisfying the Liouville-von Neumann equation.
A master equation for a quantum system coupled to a heat bath with stochastically fluctuating energy levels is derived by making use of the ensemble averaging and the averaging with respect to a stochastic process in the bath. Relaxation terms are determined in the Born approximation with respect to the system-bath interaction and the damping parameters related to a relaxation kernel are specified. In parallel with the spectral strength of the bath, the damping parameters determine the transient times for the Markovian description creating the physical origin of the slippage [A. Suarez, R. Sibey, and I. Oppenheim, J. Chem. Phys. 97, 5101 (1992)]. The influence of energy fluctuations of the bath is analyzed for a two-level system including the solution of the corresponding non-Markovian equation for the level population difference. The conditions for the formation of Boltzmann's thermal ratio between steady-state populations are evaluated as well.