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Physical review. E, Statistical physics, plasmas, fluids, and related interdisciplinary topics

Real-time path-integral approach to quantum coherence and dephasing in nonadiabatic transitions and nonlinear optical response

Yoshitaka Tanimura, Shaul Mukamel

Published Jan 1, 1993• 132 citations
Publisher

Abstract

Quantum coherence and its destruction (dephasing) by coupling to a dissipative environment plays an important role in time-resolved nonlinear optical response as well as nonadiabatic transitions and tunneling processes in condensed phases. Generating functions of density-matrix elements and multitime coordinate and momentum correlation functions related to these phenomena are calculated using a pathintegral approach by performing functional integration. The dissipative environment is assumed to be an ensemble of harmonic oscillators and is taken into account by using Feynman-Vernon influence functional. Closed-form expressions for generating functions in terms of the bath spectral density are derived. The present theory generalizes earlier calculations of these quantities to arbitrary temperatures, any dependence of the transition coupling on coordinates (non-Condon effects), and arbitrary order in the interstate coupling. Conditions for factorizing the Liouville-space generating functions that allow a reduced description based on the classical Langevin equation are established. Possible applications to four-wave-mixing spectroscopy and nonadiabatic rate processes are discussed.

DOI
10.1103/physreve.47.118

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Quantum coherence and its destruction (dephasing) by coupling to a dissipative environment plays an important role in time-resolved nonlinear optical response as well as nonadiabatic transitions and tunneling processes in condensed phases. Generating functions of density-matrix elements and multitime coordinate and momentum correlation functions related to these phenomena are calculated using a pathintegral approach by performing functional integration. The dissipative environment is assumed to be an ensemble of harmonic oscillators and is taken into account by using Feynman-Vernon influence functional. Closed-form expressions for generating functions in terms of the bath spectral density are derived. The present theory generalizes earlier calculations of these quantities to arbitrary temperatures, any dependence of the transition coupling on coordinates (non-Condon effects), and arbitrary order in the interstate coupling. Conditions for factorizing the Liouville-space generating functions that allow a reduced description based on the classical Langevin equation are established. Possible applications to four-wave-mixing spectroscopy and nonadiabatic rate processes are discussed.
In this thesis the path integral formalism is applied to the calculation of the dynamics of dissipative quantum systems. The time evolution of a system of bilinearly coupled bosonic modes is treated using the real-time path integral technique in coherent-state representation. This method is applied to a damped harmonic oscillator within the Caldeira-Leggett model. In order to get the stationary trajectories the corresponding Lagrangian function is diagonalized and then the path integrals are evaluated by means of the stationary-phase method. The time evolution of the reduced density matrix in the basis of coherent states is given in simple analytic form for weak system-bath coupling, i.e. the so-called rotating-wave terms can be evaluated exactly but the non-rotating-wave terms only in a perturbative manner. The validity range of the rotating-wave approximation is discussed from the viewpoint of spectral equations. In addition, it is shown that systems without initial system-bath correlations can exhibit initial jumps in the population dynamics even for rather weak dissipation. Only with initial correlations the classical trajectories for the system coordinate can be recovered. The path integral formalism in a combined phase-space and coherent-state representation is applied to the problem of curve-crossing dynamics. The system of interest is described by two coupled one-dimensional harmonic potential energy surfaces interacting with a heat bath. The mapping approach is used to rewrite the Lagrangian function of the electronic part of the system. Using the Feynman-Vernon influence-functional method the bath is eliminated whereas the non-Gaussian part of the path integral is treated using the perturbation theory in the small coordinate shift between potential energy surfaces. The vibrational and the population dynamics is considered in a lowest order of the perturbation. The dynamics of a Gaussian wave packet is analyzed along a one-dimensional reaction coordinate. Also the damping rate of coherence in the electronic part of the relevant system is evaluated within the ordinary and variational perturbation theory. The analytic expressions for the rate functions are obtained in the low and high temperature regimes.
Recent progress in numerical methods for evaluating the real-time path integral in dissipative harmonic environments is reviewed. Quasi-adiabatic propagators constructed numerically allow convergence of the path integral with large time increments. Integration of the harmonic bath leads to path integral expressions that incorporate the exact dynamics of the quantum particle along the adiabatic path, with an influence functional that describes nonadiabatic corrections. The resulting quasi-adiabatic propagator path integral is evaluated by efficient system-specific quadratures in most regimes of parameter space, although some cases are handled by grid Monte Carlo sampling. Exploiting the finite span of nonlocal influence functional interactions characteristic of broad condensed phase spectra leads to an iterative scheme for calculating the path integral over arbitrary time lengths. No uncontrolled approximations are introduced, and the resulting methodology converges to the exact quantum result with modest amounts of computational power. Applications to tunneling dynamics in the condensed phase are described.
The time evolution of a system of bilinearly coupled bosonic modes is investigated using the real-time path integral technique in the coherent-state representation. In order to get the stationary trajectories, the corresponding Lagrangian function is diagonalized and then the path integrals are evaluated by means of the stationary-phase method. The present treatment is applied to a dissipative harmonic oscillator within the Caldeira–Leggett model. The time evolution of the reduced density matrix in the basis of coherent states is given in simple analytic form for weak system–bath coupling, i.e. the so-called rotating-wave terms can be evaluated exactly but the non-rotating-wave terms only in a perturbative manner. The validity range of the rotating-wave approximation is discussed from the viewpoint of spectral equations. In contrast to many perturbative approaches, the bath degrees of freedom are treated explicitly. In addition, it is shown that systems without initial system–bath correlations can exhibit initial jumps in the population dynamics even for rather weak dissipation. Only with initial correlations can the classical trajectories for the system coordinate be recovered.
A quantum-activated rate process in the presence of a nonlinear dissipative environment is studied with a Feynman path-integral technique. The nonlinear dissipation arises from specific nonlinear couplings between the reaction coordinate and a many-dimensional bath of effective harmonic oscillators. Such coupling results in a nonlinear influence functional for the effective Feynman path integral along the reaction coordinate. Large nonlinear effects on the rate constant are found at low temperatures.
We have studied the real-time dynamics of dissipative tunneling between two coupled diabatic surfaces. The interplay of tunneling, vibrational relaxation, dephasing, and resonances leads to various regimes of population dynamics, from coherent oscillations between the surfaces to exponential decay described by a rate constant. To describe these phenomena, we exploited recent efficient discretized-path-integral techniques; the two-surface system is treated exactly using a numerically constructed propagator, while the effects of the dissipative environment are incorporated through an influence functional. This procedure results in a low-dimensional integral, which is evaluated by quadrature. Use of a discrete-variable representation (DVR) allows us to replace continuous paths by paths that sample a small set of coordinate points; in particular, the conventional two-level-system approximation is shown to correspond to the limit of two DVR points. The specific features pertinent to nonadiabatic tunneling are discussed.
We consider the time correlation function of observables pertaining to a (quantum subsystem +bath), where the bath is coupled to a reservoir with many degrees of freedom. Integrating over the coordinates of this reservoir and assuming no initial correlations between the (quantum subsystem+bath) and the reservoir, we obtain an expression for the time correlation function that contains an influence functional. We then take the semiclassical and Fokker–Planck limits while modeling the reservoir with an Ohmic continuum of harmonic oscillators coupled bilinearily to the coordinates of the bath. The semiclassical limit is taken using a variant of Pechukas’ stationary phase analysis of the reduced propagator that yields a time correlation function written in terms of connected “classical” paths. These paths are got by solving the concatenation of several short-time interval Pechukas equations; as a result, the determination of these paths is more feasible than the determination of the “classical” path associated with a single long-time interval Pechukas equation. This concatenation includes the dissipative and stochastic forces associated with a classical Brownian particle. We then use decoherence arguments derived from an inspection of the influence functional to eliminate the phase interference structure of the bath. This elimination yields a mixed quantum-classical time correlation function that can be evaluated using nonadiabatic mixed quantum-classical dynamics schemes similar to those proposed recently by Webster and Tully.