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The Journal of Chemical Physics

Quantum-mechanical derivation of the Bloch equations: Beyond the weak-coupling limit

Brian B. Laird, J. Budimir, James L. Skinner

Published Mar 15, 1991• 160 citations
Publisher

Abstract

Two nondegenerate quantum levels coupled off-diagonally and linearly to a bath of quantum-mechanical harmonic oscillators are considered. In the weak-coupling limit one finds that the equations of motion for the reduced density-matrix elements separate naturally into two uncoupled pairs of linear equations for the diagonal and off-diagonal elements, which are known as the Bloch equations. The equations for the populations form the simplest two-component master equation, and the rate constant for the relaxation of nonequilibrium population distributions is 1/T1, defined as the sum of the ‘‘up’’ and ‘‘down’’ rate constants in the master equation. Detailed balance is satisfied for this master equation in that the ratio of these rate constants is equal to the ratio of the equilibrium populations. The relaxation rate constant for the off-diagonal density-matrix elements is known as 1/T2. One finds that this satisfies the well-known relation 1/T2=1/2T1. In this paper the weak-coupling limit is transcended by deriving the Bloch equations to fourth order in the coupling. The equations have the same form as in the weak-coupling limit, but the rate constants are calculated to fourth order. For the population-relaxation rate constants this results in an extension to fourth order of Fermi’s golden rule. We find that these higher-order rate constants do indeed satisfy detailed balance. Comparing the dephasing and population-relaxation rate constants, we find that in fourth order 1/T2≠1/2T1.

DOI
10.1063/1.460626

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Two nondegenerate quantum levels coupled off-diagonally and linearly to a bath of quantum-mechanical harmonic oscillators are considered. In the weak-coupling limit one finds that the equations of motion for the reduced density-matrix elements separate naturally into two uncoupled pairs of linear equations for the diagonal and off-diagonal elements, which are known as the Bloch equations. The equations for the populations form the simplest two-component master equation, and the rate constant for the relaxation of nonequilibrium population distributions is 1/T1, defined as the sum of the ‘‘up’’ and ‘‘down’’ rate constants in the master equation. Detailed balance is satisfied for this master equation in that the ratio of these rate constants is equal to the ratio of the equilibrium populations. The relaxation rate constant for the off-diagonal density-matrix elements is known as 1/T2. One finds that this satisfies the well-known relation 1/T2=1/2T1. In this paper the weak-coupling limit is transcended by deriving the Bloch equations to fourth order in the coupling. The equations have the same form as in the weak-coupling limit, but the rate constants are calculated to fourth order. For the population-relaxation rate constants this results in an extension to fourth order of Fermi’s golden rule. We find that these higher-order rate constants do indeed satisfy detailed balance. Comparing the dephasing and population-relaxation rate constants, we find that in fourth order 1/T2≠1/2T1.
Fourth-order quantum master equations (FQMEs) are derived in both time nonlocal and local forms for a general system Hamiltonian, with new detailed expressions for the fourth-order kernel, where the bath correlation functions are explicitly decoupled from the system superoperators. Further simplifications can be made for the model of linearly coupled harmonic oscillator bath. Consideration of the high temperature Ohmic bath limit leads to a general Markovian FQME with compact forms of time independent superoperators. Two examples of this equation are then considered. For the system of a quantum particle in a continuous potential field, the equation reduces to a known form of the quantum Fokker–Planck equation, except for a fourth-order potential renormalization term that can be neglected only in the weak system-bath interaction regime. For a two-level system with off-diagonal coupling to the bath, fourth-order corrections do not alter the relaxation characteristics of the second-order equation and introduce additional coherence terms in the equations for the off-diagonal elements.
The model of two nondegenerate quantum levels coupled linearly and off-diagonally to a bath of quantum mechanical harmonic oscillators studied previously by Laird, Budimir, and Skinner is re-examined. Interpretations are made for both the fourth order population relaxation and dephasing processes. Some of the methods used are applied to the standard spin-boson problem. The question of experimental detection of predicted phenomena is discussed. An approximate method, based on a canonical transformation of the original Hamiltonian is proposed to study the problem.
We construct a quantum Markovian master equation for a driven system coupled to a thermal bath. The derivation utilizes an explicit solution of the propagator of the driven system. This enables the validity of the master equation to be extended beyond the adiabatic limit. The nonadiabatic master equation (NAME) is derived employing the weak system-bath coupling limit. The NAME is valid when a separation of timescales exists between the bath dynamics and the external driving. In contrast to the adiabatic master equation, the NAME leads to coupled equations of motion for the population and coherence. We employ the NAME to solve the example of an open driven time-dependent harmonic oscillator. For the harmonic oscillator the NAME predicts the emergence of coherence associated with the dissipation term. As a result of the nonadiabatic driving the thermalization rate is suppressed. The solution is compared with both numerical calculations and the adiabatic master equation.
Abstract This chapter introduces the density operator and the Liouville equation and outlines how reduced dynamical description of open quantum systems naturally leads to the appearance of relaxation processes. (1) The density operator and the quantum Liouville equation (the density matrix for a pure system, statistical mixtures, representations, coherences, thermodynamic equilibrium). (2) An example: The time evolution of a two-level system in the density matrix formalism. (3) Reduced descriptions. (4) Time evolution equations for reduced density operators: The quantum master equation (projection operators, The Nakajima–Zwanzig equation, Derivation of the quantum master equation using the thermal projector, The quantum master equation in the interaction representation, The Markovian limit—the Redfield equation, The secular approximation and the Lindblad equation). (5) The Lindblad equation in the ‘Heisenberg representation’. (6) Relaxation of a two-level system and a harmonic oscillator revisited. (7) The optically driven two-level system in a thermal environment—the Bloch equations. (8) The oscillating dipole model of a two-level molecule. (9) Analogy of a coupled two-level system to a spin ½ system in a magnetic field.
A straightforward extension of time-dependent quantum-mechanical perturbation theory is made to obtain the equivalent formulae for a statistical mixture of states. The 'master equation' resulting from this procedure is, in its lowest order, the analogue in quantum statistics of the 'Golden Rule' for transition rates and reduces exactly to this form in the limit of pure initial states. The authors give results to fourth order and illustrate their use by applying them to the problem of the resonant interaction of an electromagnetic field and a two-level atom.
We report an alternate formulation of the quantum master equation (QME) to describe the dynamics of a quantum system weakly coupled to a heat bath, in the presence of weak external driving. A key feature of this approach is the introduction of an explicit Hamiltonian to model the thermal fluctuations in the heat bath. We show that the resulting time coarse-grained dynamical equation for the quantum system has dissipators with a natural regulator, which emerges from an ensemble average over the fluctuations. Importantly, such regularized dissipators arise from the second-order contributions of both the external drive as well as the system-environment coupling. We show that the second-order drive terms, regularized to time-scales set by the fluctuations, result in dynamic drive-induced frequency shifts as well as drive-dependent relaxation phenomena. Considering the specific case of an ensemble of two-level systems, subjected to a linearly polarized external drive, we derive the modified Bloch Equations with such drive-dependent shift and damping terms. The resulting drive-induced frequency shifts converge to the known forms of dynamic frequency shifts, such as the Bloch-Siegert shift or the dynamic Stark shift, in appropriate limits. The Kramers-Kronig pairs of these frequency shifts - manifest as drive-dependent damping terms in the modified Bloch Equations and help explain the Redfield limit of free-induction-decay (FID) rates as well as the non-Bloch decay of Rabi oscillations in isotropic medium. Our method predicts correct orders of magnitudes of non-Bloch decay rates in isotropic medium as well as their observed temperature dependence. The QME reported here, correctly describes all known aspects of the driven-dissipative dynamics up to second-order of an open quantum system with appropriate thermal signatures and as such is expected to provide deeper insights into the study of quantum information processing on real systems.