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The Journal of Physical Chemistry A

Derivation of Quantum Langevin Equation from an Explicit Molecule−Medium Treatment in Interaction Picture

Sambhu N. Datta

Published Oct 8, 2005• 3 citations

Abstract

A quantum mechanical form of the Langevin equation is derived from an explicit consideration of the molecule-medium interaction, as advocated by Simons in 1978, and by using two identities in the interaction picture. This can be easily reduced to the classical regime, and further simplified to the macroscopic Langevin equation by considering the stochastic Langevin force autocorrelation function. One of the so-called Einstein relations appears as a byproduct. By following the methodology proposed by Simons, an exact expression for the momentum autocorrelation function is obtained. The latter can be used to calculate the zero-frequency macroscopic diffusion coefficient that is observed to satisfy the second Einstein relation. The formalism described above gives rise to the possibility of explicitly computing the transport characteristics such as friction constant and diffusion coefficient from the corresponding quantum statistical mechanical expressions. A discussion on the Langevin equation becomes complete only when the corresponding Fokker-Planck equation is obtained. Therefore, the probability of the evolution of states with a particular absolute magnitude of linear momentum from those of another momentum eigenvalue is quantum mechanically defined. This probability appears as a special average value of a projection operator and as a special projection operator correlation function. A classical identity is introduced that is shown to be valid also for the quantum mechanically defined probability function. By using this identity, the so-called Fokker-Planck equation for the evolution probability is easily established.

DOI: 10.1021/jp053098i

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A quantum mechanical form of the Langevin equation is derived from an explicit consideration of the molecule-medium interaction, as advocated by Simons in 1978, and by using two identities in the interaction picture. This can be easily reduced to the classical regime, and further simplified to the macroscopic Langevin equation by considering the stochastic Langevin force autocorrelation function. One of the so-called Einstein relations appears as a byproduct. By following the methodology proposed by Simons, an exact expression for the momentum autocorrelation function is obtained. The latter can be used to calculate the zero-frequency macroscopic diffusion coefficient that is observed to satisfy the second Einstein relation. The formalism described above gives rise to the possibility of explicitly computing the transport characteristics such as friction constant and diffusion coefficient from the corresponding quantum statistical mechanical expressions. A discussion on the Langevin equation becomes complete only when the corresponding Fokker-Planck equation is obtained. Therefore, the probability of the evolution of states with a particular absolute magnitude of linear momentum from those of another momentum eigenvalue is quantum mechanically defined. This probability appears as a special average value of a projection operator and as a special projection operator correlation function. A classical identity is introduced that is shown to be valid also for the quantum mechanically defined probability function. By using this identity, the so-called Fokker-Planck equation for the evolution probability is easily established.

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Quantum diffusion equations featuring explicitly time-dependent transport coefficients are derived from generalized non-Markovian Langevin equations. Generalized fluctuation-dissipation relations and analytic expressions for calculating the friction and diffusion coefficients in nuclear processes are obtained. The asymptotic behavior of the transport coefficients and correlation functions for a damped harmonic oscillator that is linearly coupled in momentum to a heat bath is studied. The coupling to a heat bath in momentum is responsible for the appearance of the diffusion coefficient in coordinate. The problem of regression of correlations in quantum dissipative systems is analyzed.

We first point out that nonrelativistic quantum mechanics formulated at imaginary time s = it can formally be recognized as the Fokker-Planck description of a classical Brownian motion, which occurs (in general) in a medium where particles are absorbed and emitted. We next offer a new formulation of quantum dynamics, which is basically the Langevin treatment of that Brownian motion. More explicitly, we derive a noise average representation of the transition probability W ( X", s"|X', s' ) in terms of the solutions to a Langevin equation with a Gaussian white noise. Upon analytic continuation back to real time W ( X", s"|X', s' ) becomes the propagator of the original Schrödinger equation, namely we have ⟨ X", t"|X', t' ⟩ = W ( X", it"|X', it' ). The main advantage of this approach is to permit a systematic application to quantum-dynamical problems of the mathematical techniques developed in the theory of classical stochastic processes, even when vector potentials and/or time-dependent potentials are present.

We again note that Langevin equations written for observables (– operators in quantum mechanics) conform to the Heisenberg view. On the other hand, an entity that embodies the wave function of the Schrödinger picture is the von Neumann density operator, usually denoted by t( )ρ , whose classical counterpart is the probability distribution function (pdf) discussed earlier. It is helpful to introduce a formalism for the pdf completely at par with the Langevin description. The resultant Fokker-Planck (FP) equations serve as the subjects of this chapter. The simplest FP equation can be derived from the master equation (2.25) for a stationary Markov process, as shown below (Agarwal 1983, Risken 1996).

We systematically derive the quantum generalized nonlinear Langevin equation using Morozov's projection operator method. This approach extends the linear Mori-Zwanzig projection operator technique, allowing for the inclusion of nonlinear interactions among macroscopic modes. Additionally, we obtain the quantum generalized Fokker-Planck equation within the Heisenberg picture, which is consistent with Morozov's original formulation. These equations are fundamentally significant in nonequilibrium statistical physics, particularly in scenarios characterized by enhanced fluctuations, such as anomalous transport phenomena near critical points. The quantum nature of the derived generalized Langevin and Fokker-Planck equations is anticipated to provide a more detailed description than their classical equivalents. Specifically, the noise kernel in the quantum generalized Langevin equation is multiplicative, which broadens the applicability beyond Gaussian approximations. Given specific interactions, these equations are expected to be instrumental in investigating critical transport phenomena.

We derive a

c

-number generalized Langevin equation (GLE) describing the evolution of the expectation values ${\ensuremath{\langle}{x}_{i}\ensuremath{\rangle}}_{t}$ of the atomic position operators

{x}_{i}

of an open system. The latter is coupled linearly to a harmonic bath kept at a fixed temperature. The equations of motion contain a non-Markovian friction term with the classical kernel [L. Kantorovich, Phys. Rev. B 78, 094304 (2008)] and a zero mean non-Gaussian random force with correlation functions that depend on the initial preparation of the open system. We used a density operator formalism without assuming that initially the combined system was decoupled. The only approximation made in deriving quantum GLE consists of assuming that the Hamiltonian of the open system at time

t

can be expanded up to the second order with respect to operators of atomic displacements ${u}_{i}={x}_{i}\ensuremath{-}{\ensuremath{\langle}{x}_{i}\ensuremath{\rangle}}_{t}$ in the open system around their exact atomic positions ${\ensuremath{\langle}{x}_{i}\ensuremath{\rangle}}_{t}$ (the ``harmonization'' approximation). The noise is introduced to ensure that sampling many quantum GLE trajectories yields exactly the average one. An explicit expression for the pair correlation function of the noise, consistent with the classical limit, is also proposed. Unlike the usually considered quantum operator GLE, the proposed

c

-number quantum GLE can be used in direct molecular dynamic simulations of open systems under general equilibrium or nonequilibrium conditions.