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The Journal of Physical Chemistry A

Semigroup Representations, Site Couplings, and Relaxation in Quantum Systems

William B. Davis, Michael R. Wasielewski, Ronnie Kosloff, Mark A. Ratner

Published Sep 30, 1998• 31 citations
Publisher

Abstract

The semigroup formalism permits a general description of relaxation processes in quantum mechanical systems coupled to Markovian baths. From its definition, the semigroup formalism should be expressed in terms of the dissipative and relaxation coupling of the eigenstates of the quantum system to the bath modes. Often, for convenience both in calculation and in physical interpretation, it is more straightforward to couple local states of the quantum mechanical system to the bath. Within a simple two-site system, we examine the generalities of these two different coupling schemes, noting situations in which they are the same and situations for which substantial differences occur.

DOI
10.1021/jp9813544

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The semigroup formalism permits a general description of relaxation processes in quantum mechanical systems coupled to Markovian baths. From its definition, the semigroup formalism should be expressed in terms of the dissipative and relaxation coupling of the eigenstates of the quantum system to the bath modes. Often, for convenience both in calculation and in physical interpretation, it is more straightforward to couple local states of the quantum mechanical system to the bath. Within a simple two-site system, we examine the generalities of these two different coupling schemes, noting situations in which they are the same and situations for which substantial differences occur.
Quantum dissipation involves both energy relaxation and decoherence, leading toward quantum thermal equilibrium. There are several theoretical prescriptions of quantum dissipation but none of them is simple enough to be treated exactly in real applications. As a result, formulations in different prescriptions are practically used with different approximation schemes. This review examines both theoretical and application aspects on various perturbative formulations, especially those that are exact up to second-order but nonequivalent in high-order system-bath coupling contributions. Discrimination is made in favor of an unconventional formulation that in a sense combines the merits of both the conventional time-local and memory-kernel prescriptions, where the latter is least favorite in terms of the applicability range of parameters for system-bath coupling, non-Markovian, and temperature. Also highlighted is the importance of correlated driving and dissipation effects, not only on the dynamics under strong external field driving, but also in the calculation of field-free correlation and response functions.
The dynamical study of chemical systems whose evolution is governed by quantum mechanics can now be computed fairly effectively for small systems in which the evolution is entirely Hamiltonian. When such Hamiltonian systems interact with their environment, however, relaxation and dephasing terms are introduced into the evolution. To include the effect of these terms, several methods are in current use. This paper is devoted to an exposition, analysis, and several simple applications of the semigroup technique for dealing with these non-Hamiltonian evolution terms. We discuss the nature of the semigroup terms, how they arise and how they are applied, and some of their advantages and disadvantages compared to other methods including dissipation. Specific applications to three simple two-site problems are given.
We investigate the effect of inter-mode coupling on the vibrational relaxation dynamics of molecules in weak dissipative environments. The simulations are performed within the reduced density matrix formalism in the Markovian regime, assuming a Lindblad form for the system-bath interaction. The prototypical two-dimensional model system representing two CO molecules approaching a Cu(100) surface is adapted from an ab initio potential, while the diatom-diatom vibrational coupling strength is systematically varied. In the weak system-bath coupling limit and at low temperatures, only first order non-adiabatic uni-modal coupling terms contribute to surface-mediated vibrational relaxation. Since dissipative dynamics is non-unitary, the choice of representation will affect the evolution of the reduced density matrix. Two alternative representations for computing the relaxation rates and the associated operators are thus compared: the fully coupled spectral basis, and a factorizable ansatz. The former is well-established and serves as a benchmark for the solution of Liouville-von Neumann equation. In the latter, a contracted grid basis of potential-optimized discrete variable representation is tailored to incorporate most of the inter-mode coupling, while the Lindblad operators are represented as tensor products of one-dimensional operators, for consistency. This procedure results in a marked reduction of the grid size and in a much more advantageous scaling of the computational cost with respect to the increase of the dimensionality of the system. The factorizable method is found to provide an accurate description of the dissipative quantum dynamics of the model system, specifically of the time evolution of the state populations and of the probability density distribution of the molecular wave packet. The influence of intra-molecular vibrational energy redistribution appears to be properly taken into account by the new model on the whole range of coupling strengths. It demontrates that most of the mode mixing during relaxation is due to the potential part of the Hamiltonian and not to the coupling among relaxation operators.
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.
We consider the quantum evolution and relaxation of an electron or hole which is coupled to a set of bath modes. In most applications the bath modes would be the vibronic coordinates but the model considered applies to any type of dynamic boson environment. The method is developed specifically for the problem of dynamic polaron formation in small nonperiodic systems. It can describe a broad group of experimental situations, including in particular electron localization in organics and polymeric materials and devices. The immediate bath is allowed to dissipate energy to a secondary bath. The bath obeys classical dynamics which puts some restriction on the range of validity of this approach. Using the density matrix formalism on a tight binding model consisting of a linear chain coupled to vibronic coordinates, we demonstrate in real time how the interaction with a dissipative bath makes the initial quantum distribution reach a steady-state population. This calculation is based on the Ehrenfest dynamics approximation. As an example we consider coupling at a single impurity site and find that for given parameters (bath coupling, site energy, and relaxation rate), the particle becomes dynamically localized in space on a particular time scale. This localized particle can be called a polaron. We define a population formation time in the same way as done in the experimental measurement. This formation time is studied as a function of the coupling strength, bandwidth, and energy dissipation rate. Energy dissipation plays a crucial role in the spatial localization process. The formation time shortens as the electron-vibration coupling increases, and as the intersite tunneling increases, but lengthens with impurity trap depth. Polaron formation is suppressed for sufficiently wide electronic bands.
We study relaxation dynamics in a strongly interacting two-site Fermi-Hubbard model that is induced by coupling each site to a local fermionic bath. To derive the proper form of the Lindblad operators that enter an effective description of the system-bath coupling in different temperature regimes, we employ a diagrammatic real-time technique for the time evolution of the reduced density matrix. In spite of a local coupling to the baths, the found Lindblad operators are nonlocal in space. We compare with the local approximation, where those nonlocal effects are neglected. Furthermore, we propose an improvement on the commonly used secular approximation (rotating-wave approximation), referred to as coherent approximation, which turns out superior in all studied parameter regimes (and equivalent otherwise). We look at the relaxation dynamics for several important observables and compare the methods for early and late times in various temperature regimes.