Challenges
Datasets
Workspaces
Papers
Discussions
Leaderboard
Log inSign up
Challenges
Datasets
Workspaces
Papers
Discussions
Leaderboard
Blog
Job Board
Q3AS

© 2026 Aqora Quantum S.A.S.

TermsPrivacyLegal Notice

The Journal of Chemical Physics

A temperature-dependent Schrödinger equation based on a time-dependent self consistent field approximation

Uri Peskin, Michal Steinberg

Published Jul 8, 1998• 19 citations
Publisher

Abstract

A temperature-dependent Schrödinger equation is proposed for the study of quantum dynamics in systems which interact with an external bath. The derivation is based on a time-dependent self consistent field (TDSCF) approximation for a system-bath wave function. As previously shown by Miller, this approximation leads to a quantum mechanical analog to the classical generalized Langevin equation. By replacing the time-evolution of the quantum mechanical bath observables with the corresponding classical trajectories, the fluctuating force and the nonlinear friction kernel in the Langevin-Schrödinger equation become temperature-dependent where the fluctuations intensity is proportional to T. Application of the new equation to the spin-boson model shows agreement with numerically exact path integral calculations for T>0. We relate the success of the TDSCF approximation in this case to the bath-induced noise which diminishes the importance of quantum mechanical system-bath correlations.

DOI
10.1063/1.476609

Related papers

Path integral density matrix dynamics: A method for calculating time-dependent properties in thermal adiabatic and non-adiabatic systems

Scott Habershon

We introduce a new approach for calculating quantum time-correlation functions and time-dependent expectation values in many-body thermal systems; both electronically adiabatic and non-adiabatic cases can be treated. Our approach uses a path integral simulation to sample an initial thermal density matrix; subsequent evolution of this density matrix is equivalent to solution of the time-dependent Schrödinger equation, which we perform using a linear expansion of Gaussian wavepacket basis functions which evolve according to simple classical-like trajectories. Overall, this methodology represents a formally exact approach for calculating time-dependent quantum properties; by introducing approximations into both the imaginary-time and real-time propagations, this approach can be adapted for complex many-particle systems interacting through arbitrary potentials. We demonstrate this method for the spin Boson model, where we find good agreement with numerically exact calculations. We also discuss future directions of improvement for our approach with a view to improving accuracy and efficiency.

The Journal of Chemical Physics•Sep 12, 2013•8 citations

On the generalized Langevin equation: Classical and quantum mechanicala)

Emilio Cortés, Bruce J. West, Katja Lindenberg

The generalized Langevin equation and its attendant fluctuation–dissipation relation (FDR) for both classical and quantum systems is explictly derived for a large class of system-bath interaction potentials. We demonstrate for this class of potentials that the classical FDR involving only the temperature of the bath is satisfied, and that in general the decay times of the dissipative processes and of the system are temperature dependent. We also demonstrate that the quantum FDR depends in detail on the nature of the bath and on the specific system-bath interaction. Thus we conclude that while the classical Langevin equation is phenomenologically useful, its quantum counterpart is much more limited.

The Journal of Chemical Physics•Mar 15, 1985•215 citations

Second-quantized molecular time scale generalized Langevin equation theory and the quantum oscillator

H. Keith McDowell

The short-time Gaussian approximation to the molecular time scale generalized Langevin equation (MTGLE) friction kernel is introduced and used to compute the time dependence of a fluctuation time correlation function. The fluctuations are shown to have two time scales, namely, the dissipation time scale and a quantum time scale given by exp[−2πkTt/ℏ]. Absorption and emission spectral functions for a quantum oscillator coupled to a bath are derived with no approximations made. The second-quantized MTGLE approach is applied to the problem of a quantum oscillator coupled linearly to a bath of quantum oscillators. The method is shown to be consistent with previous work and to provide a systematic methodology to examine more general many-body boson problems.

The Journal of Chemical Physics•Oct 15, 1987•10 citations

Exact c -Number Representation of Non-Markovian Quantum Dissipation

Jürgen T. Stockburger, Hermann Grabert

The reduced dynamics of a quantum system interacting with a linear heat bath finds an exact representation in terms of a stochastic Schrödinger equation. All memory effects of the reservoir are transformed into noise correlations and mean-field friction. The classical limit of the resulting stochastic dynamics is shown to be a generalized Langevin equation, and conventional quantum state diffusion is recovered in the Born-Markov approximation. The non-Markovian exact dynamics, valid at arbitrary temperature and damping strength, is exemplified by an application to the dissipative two-state system.

arXiv:cond-mat/0203193•Physical Review Letters•Apr 15, 2002•253 citations

c -number quantum generalized Langevin equation for an open system

Lev N Kantorovich, H. Ness, Lorenzo Stella +1 more

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.

arXiv:1607.02343•Physical review. B./Physical review. B•Nov 8, 2016•9 citations

A semiclassical self-consistent-field approach to dissipative dynamics: The spin–boson problem

Gerhard Stock

A semiclassical time-dependent self-consistent-field approach for the description of dissipative quantum phenomena is proposed. The total density operator is approximated by a semiclassical ansatz, which couples the system degrees of freedom to the bath degrees of freedom in a self-consistent manner, and is thus in the spirit of a classical-path description. The capability of the approach is demonstrated by comparing semiclassical calculations for a spin–boson model with an Ohmic bath to exact path-integral calculations. It is shown that the semiclassical model nicely reproduces the complex dissipative behavior of the spin–boson model for a large range of model parameters. The validity and accuracy of the semiclassical approach is discussed in some detail. It is shown that the method is essentially based on the assumption of complete randomization of nuclear phases. In particular, the assumption of phase randomization allows one to perform the trace over the bath variables through quasiclassical sampling of the nuclear initial conditions without invoking any further approximation.

The Journal of Chemical Physics•Jul 22, 1995•113 citations
A temperature-dependent Schrödinger equation is proposed for the study of quantum dynamics in systems which interact with an external bath. The derivation is based on a time-dependent self consistent field (TDSCF) approximation for a system-bath wave function. As previously shown by Miller, this approximation leads to a quantum mechanical analog to the classical generalized Langevin equation. By replacing the time-evolution of the quantum mechanical bath observables with the corresponding classical trajectories, the fluctuating force and the nonlinear friction kernel in the Langevin-Schrödinger equation become temperature-dependent where the fluctuations intensity is proportional to T. Application of the new equation to the spin-boson model shows agreement with numerically exact path integral calculations for T>0. We relate the success of the TDSCF approximation in this case to the bath-induced noise which diminishes the importance of quantum mechanical system-bath correlations.
We introduce a new approach for calculating quantum time-correlation functions and time-dependent expectation values in many-body thermal systems; both electronically adiabatic and non-adiabatic cases can be treated. Our approach uses a path integral simulation to sample an initial thermal density matrix; subsequent evolution of this density matrix is equivalent to solution of the time-dependent Schrödinger equation, which we perform using a linear expansion of Gaussian wavepacket basis functions which evolve according to simple classical-like trajectories. Overall, this methodology represents a formally exact approach for calculating time-dependent quantum properties; by introducing approximations into both the imaginary-time and real-time propagations, this approach can be adapted for complex many-particle systems interacting through arbitrary potentials. We demonstrate this method for the spin Boson model, where we find good agreement with numerically exact calculations. We also discuss future directions of improvement for our approach with a view to improving accuracy and efficiency.
The generalized Langevin equation and its attendant fluctuation–dissipation relation (FDR) for both classical and quantum systems is explictly derived for a large class of system-bath interaction potentials. We demonstrate for this class of potentials that the classical FDR involving only the temperature of the bath is satisfied, and that in general the decay times of the dissipative processes and of the system are temperature dependent. We also demonstrate that the quantum FDR depends in detail on the nature of the bath and on the specific system-bath interaction. Thus we conclude that while the classical Langevin equation is phenomenologically useful, its quantum counterpart is much more limited.
The short-time Gaussian approximation to the molecular time scale generalized Langevin equation (MTGLE) friction kernel is introduced and used to compute the time dependence of a fluctuation time correlation function. The fluctuations are shown to have two time scales, namely, the dissipation time scale and a quantum time scale given by exp[−2πkTt/ℏ]. Absorption and emission spectral functions for a quantum oscillator coupled to a bath are derived with no approximations made. The second-quantized MTGLE approach is applied to the problem of a quantum oscillator coupled linearly to a bath of quantum oscillators. The method is shown to be consistent with previous work and to provide a systematic methodology to examine more general many-body boson problems.
The reduced dynamics of a quantum system interacting with a linear heat bath finds an exact representation in terms of a stochastic Schrödinger equation. All memory effects of the reservoir are transformed into noise correlations and mean-field friction. The classical limit of the resulting stochastic dynamics is shown to be a generalized Langevin equation, and conventional quantum state diffusion is recovered in the Born-Markov approximation. The non-Markovian exact dynamics, valid at arbitrary temperature and damping strength, is exemplified by an application to the dissipative two-state system.
We derive a ccc-number generalized Langevin equation (GLE) describing the evolution of the expectation values ${\ensuremath{\langle}{x}_{i}\ensuremath{\rangle}}_{t}$ of the atomic position operators xi{x}_{i}xi​ 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 ttt 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 ccc-number quantum GLE can be used in direct molecular dynamic simulations of open systems under general equilibrium or nonequilibrium conditions.
A semiclassical time-dependent self-consistent-field approach for the description of dissipative quantum phenomena is proposed. The total density operator is approximated by a semiclassical ansatz, which couples the system degrees of freedom to the bath degrees of freedom in a self-consistent manner, and is thus in the spirit of a classical-path description. The capability of the approach is demonstrated by comparing semiclassical calculations for a spin–boson model with an Ohmic bath to exact path-integral calculations. It is shown that the semiclassical model nicely reproduces the complex dissipative behavior of the spin–boson model for a large range of model parameters. The validity and accuracy of the semiclassical approach is discussed in some detail. It is shown that the method is essentially based on the assumption of complete randomization of nuclear phases. In particular, the assumption of phase randomization allows one to perform the trace over the bath variables through quasiclassical sampling of the nuclear initial conditions without invoking any further approximation.