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

International Journal of Quantum Chemistry

Quantum‐classical path integral: A rigorous approach to condensed phase dynamics

Nancy Makri

Published Jul 29, 2015• 71 citations
Publisher

Abstract

A rigorous methodology that combines a fully quantum mechanical treatment of a small system with a classical trajectory description of a large number of degrees of freedom is discussed in connection with the mechanism of decoherence. The need for mean field approximations in traditional quantum‐classical calculations is removed by abandoning the delocalized wavefunction description of the quantum particle in favor of Feynman's formulation, which is based on local paths. The effects of the environment enter the quantum‐classical path integral (QCPI) expression in terms of phase factors along classical trajectories, whose number grows exponentially with the number of time steps. It is argued that memory loss allows termination of trajectory branching and that the main contribution to decoherence arises from a single classical trajectory (from each sampled initial condition). Exploiting these ideas allows a dramatic reduction in the required number of trajectories, making QCPI calculations feasible. © 2015 Wiley Periodicals, Inc.

DOI
10.1002/qua.24975

Related papers

Small Matrix Quantum-Classical Path Integral

Sohang Kundu, Nancy Makri

The quantum-classical path integral (QCPI) is a rigorous formulation of nonadiabatic dynamics, where the dynamical interaction between a quantum system and its environment is captured consistently through classical trajectories driven by forces along quantum paths of the system. In this Letter, we develop a small matrix decomposition (SMatQCPI) that eliminates the tensor storage requirements of the iterative QCPI algorithm. In the case of a system coupled to a harmonic bath, SMatQCPI provides fully quantum mechanical propagation, which also reduces the computational cost to that of a single QCPI step. Further, the SMatQCPI matrices only need to account for quantum contributions to decoherence, allowing high efficiency in challenging regimes of incoherent dynamics. Overall, this new composite algorithm combines the best features of two powerful path integral formulations and offers a versatile tool for simulating condensed phase quantum dynamics.

The Journal of Physical Chemistry Letters•Apr 13, 2022•8 citations

Path integral methods for quantum dynamics in condensed phases

Tuseeta Banerjee

Quantum mechanical effects play an important role in dynamics of condensed phases. It is also well known that the difficulty of solving the full Schrödinger equation grows exponentially with time. One approach to cope up with this difficulty is to restrict quantum treatment to a few particles (system) and treat the dynamics of the rest of particles (bath) using classical trajectories. Path integral methods due to their trajectory like nature provide excellent tool to develop quantum-classical methods, but to capture long time dynamics, the number of classical trajectories grow exponentially. A part of this work focuses on improving Quantum-Classical Path Integral (QCPI) treatments that allow for larger path integral time step by building “smarter” propagators. These improved solvent-driven reference propagators is developed by incorporating physically motivated approximations to the solvent. When used in QCPI expression they allow convergence with larger time steps leading to an exponential reduction of the number of trajectories required. Further advantages of these propagators include improvements in path filtering techniques, smaller number of path integral steps for achieving the memory decoherence time, and smoothing of the integrand which leads to convergence with fewer Monte Carlo sample points. These ideas have been validated on the spin boson model - a prototypical model to study condensed phase dynamics, which consists of a two-level system coupled to a harmonic bath. The new approach of building the reference propagators combined with their iterative evaluation and filtering is validated using parameters that mimic the first electron transfer in wild-type photosynthetic reaction centres. A real-world dynamical simulation contains various anharmonic effects, Ferrocene (donor) - Ferrocenium (acceptor) system in liquid Benzene was studied where the anharmonic effects of the bath of liquid Benzene on the dynamics of the system were treated using Ensemble Averaged Classical Path. The process of electron or proton transfer occurs between two species having different charges and fluctuations in the solvent plays a key role in determining the rates of such reaction dynamics. To correctly account for the effects of initial distribution of the solvent on the dynamics of the quantum system, the concept of equilibrating the bath to the donor state of the system is used. Two different approaches have been used within the influence functional framework.

•Dec 2, 2015•0 citations

Quantum-to-classical transition and the emergence of trajectory level Darwinism with measurements distributed in time: a path integral approach

Arora, Harsh, Bishal Kumar Das, Baladitya Suri +1 more

We present a formulation for the emergence of classical dynamics in a quantum world using a path integral approach that incorporates continuous measurements. Our approach complements decoherence and coarse-grained quantum-to-classical transition frameworks. The path-integral formulation provides the joint statistics of a sequence of measurements, with each Feynman path picking up an additional random phase. Its magnitude is proportional to the measurement strength, and we give conditions under which the dominant contribution to the probability amplitude comes from trajectories near classical paths. Information proliferates across the environment, a key feature of quantum Darwinism, via plane-wave probe scattering. Extending to repeated measurements, we show that in the continuous limit each system trajectory picks up an additional phase due to momentum kicks from the probes--the origin of the back-action force. We provide conditions under which measurements yield enough ``which-path'' information while keeping the wave packet localized. This allows the quantum-to-classical transition to be described from individual measurement records, complementing the ensemble description from density matrices. We further show that the same scattering that decoheres a trajectory heats it, tying decoherence and measurement back-action together. This bounds how redundantly an individual classical trajectory can be recorded before back-action randomises it into Brownian motion. For a trapped particle, the ceiling is fixed by the resolution measured in units of the zero-point motion. It is not restrictive for macroscopic systems; it collapses to a single record where the semiclassical description of a trajectory fails, delimiting the regime in which objective classical trajectories exist. The deterministic-to-Brownian crossover is accessible in levitated optomechanics.

arXiv:2505.16889•May 22, 2025•0 citations

Boundary conditions: The path integral approach

M. Asorey, Jesús Clemente-Gallardo, J. M. Munõz-Castañeda

The path integral approach to quantum mechanics requires a substantial generalisation to describe the dynamics of systems confined to bounded domains. Nonlocal boundary conditions can be introduced in Feynman's approach by means of boundary amplitude distributions and complex phases to describe the quantum dynamics in terms of the classical trajectories. The different prescriptions involve only trajectories reaching the boundary and correspond to different choices of boundary conditions of selfadjoint extensions of the Hamiltonian. One dimensional particle dynamics is analysed in detail.

arXiv:0712.4353•Journal of Physics Conference Series•Nov 1, 2007•12 citations

The Feynman path integral

Belal Ehsan Baaquie

A path , in general, is defined by a determinate trajectory in time, from an initial to a final point. The classical trajectory is only one of the possible trajectories, and in quantum mechanics all the possible paths between the initial and final point come into play. Recall that the probability amplitude is a complex number that is assigned to each determinate path. Indeterminate paths are defined as a collection of determinate paths that are experimentally indistinguishable . In the Dirac–Feynman approach, the inherent indeterminacy of the quantum entity is realized by the degree of freedom – in undergoing time evolution – “taking” indeterminate paths [Baaquie (2013e)]. For a quantum degree of freedom evolving from an observed initial state to the observed final state – and with no other observations made – the Feynman path integral is a mathematical construction that computes the probability amplitudes by summing over all the allowed determinate paths of the degree of freedom – discussed in Feynman and Hibbs (1965), Zinn-Justin (1993), Zinn-Justin (2005) and Baaquie (2013e). Probability amplitude and time evolution Recall that the description of a quantum system, at a particular instant,isgiven by its state vector, namely |ψ>. To avoid confusion with the concept of a state vector, the term probability amplitude is used for describing a quantum entity undergoing transitions in time.

Cambridge University Press eBooks•Mar 27, 2014•0 citations

The energy-conserving dynamics of quantum-classical systems based on quantum trajectories

Sophya V. Garashchuk, M. V. Volkov

The method, described in the paper, incorporates ideas of the Bohmian formulation of quantum mechanics into a trajectory approach designed for systems comprised of light (quantum) and heavy (nearly classical) particles. The goal is to treat all degrees of freedom on the same footing but, for practical reasons, to include the quantum-mechanical effects into dynamics for just the light particles. The total wavefunction, taken as a product of slow and fast components representing the heavy and light particles respectively is represented in terms of trajectories. The fast component depends on the trajectory-guided configurations of the heavy particles. The initial conditions for the trajectories are defined by the full-dimensional initial wavefunction according to Bohm's prescription of associating the trajectory momentum with the gradient of the wavefunction phase. The time-dependent Schrödinger equation is solved for the quantum degrees of freedom using an ensemble of the quantum trajectories (or other time-propagation method) for each guiding trajectory of the classical subspace. Neglect of the quantum force acting on the heavy particles allows decoupling of the quantum calculations associated with different guiding trajectories. The approach allows reconstruction of the full-dimensional wavefunction and conserves the total wavefunction energy as illustrated for the vibrationally non-adiabatic model.

Molecular Physics•Apr 26, 2012•14 citations
A rigorous methodology that combines a fully quantum mechanical treatment of a small system with a classical trajectory description of a large number of degrees of freedom is discussed in connection with the mechanism of decoherence. The need for mean field approximations in traditional quantum‐classical calculations is removed by abandoning the delocalized wavefunction description of the quantum particle in favor of Feynman's formulation, which is based on local paths. The effects of the environment enter the quantum‐classical path integral (QCPI) expression in terms of phase factors along classical trajectories, whose number grows exponentially with the number of time steps. It is argued that memory loss allows termination of trajectory branching and that the main contribution to decoherence arises from a single classical trajectory (from each sampled initial condition). Exploiting these ideas allows a dramatic reduction in the required number of trajectories, making QCPI calculations feasible. © 2015 Wiley Periodicals, Inc.
The quantum-classical path integral (QCPI) is a rigorous formulation of nonadiabatic dynamics, where the dynamical interaction between a quantum system and its environment is captured consistently through classical trajectories driven by forces along quantum paths of the system. In this Letter, we develop a small matrix decomposition (SMatQCPI) that eliminates the tensor storage requirements of the iterative QCPI algorithm. In the case of a system coupled to a harmonic bath, SMatQCPI provides fully quantum mechanical propagation, which also reduces the computational cost to that of a single QCPI step. Further, the SMatQCPI matrices only need to account for quantum contributions to decoherence, allowing high efficiency in challenging regimes of incoherent dynamics. Overall, this new composite algorithm combines the best features of two powerful path integral formulations and offers a versatile tool for simulating condensed phase quantum dynamics.
Quantum mechanical effects play an important role in dynamics of condensed phases. It is also well known that the difficulty of solving the full Schrödinger equation grows exponentially with time. One approach to cope up with this difficulty is to restrict quantum treatment to a few particles (system) and treat the dynamics of the rest of particles (bath) using classical trajectories. Path integral methods due to their trajectory like nature provide excellent tool to develop quantum-classical methods, but to capture long time dynamics, the number of classical trajectories grow exponentially. A part of this work focuses on improving Quantum-Classical Path Integral (QCPI) treatments that allow for larger path integral time step by building “smarter” propagators. These improved solvent-driven reference propagators is developed by incorporating physically motivated approximations to the solvent. When used in QCPI expression they allow convergence with larger time steps leading to an exponential reduction of the number of trajectories required. Further advantages of these propagators include improvements in path filtering techniques, smaller number of path integral steps for achieving the memory decoherence time, and smoothing of the integrand which leads to convergence with fewer Monte Carlo sample points. These ideas have been validated on the spin boson model - a prototypical model to study condensed phase dynamics, which consists of a two-level system coupled to a harmonic bath. The new approach of building the reference propagators combined with their iterative evaluation and filtering is validated using parameters that mimic the first electron transfer in wild-type photosynthetic reaction centres. A real-world dynamical simulation contains various anharmonic effects, Ferrocene (donor) - Ferrocenium (acceptor) system in liquid Benzene was studied where the anharmonic effects of the bath of liquid Benzene on the dynamics of the system were treated using Ensemble Averaged Classical Path. The process of electron or proton transfer occurs between two species having different charges and fluctuations in the solvent plays a key role in determining the rates of such reaction dynamics. To correctly account for the effects of initial distribution of the solvent on the dynamics of the quantum system, the concept of equilibrating the bath to the donor state of the system is used. Two different approaches have been used within the influence functional framework.
We present a formulation for the emergence of classical dynamics in a quantum world using a path integral approach that incorporates continuous measurements. Our approach complements decoherence and coarse-grained quantum-to-classical transition frameworks. The path-integral formulation provides the joint statistics of a sequence of measurements, with each Feynman path picking up an additional random phase. Its magnitude is proportional to the measurement strength, and we give conditions under which the dominant contribution to the probability amplitude comes from trajectories near classical paths. Information proliferates across the environment, a key feature of quantum Darwinism, via plane-wave probe scattering. Extending to repeated measurements, we show that in the continuous limit each system trajectory picks up an additional phase due to momentum kicks from the probes--the origin of the back-action force. We provide conditions under which measurements yield enough ``which-path'' information while keeping the wave packet localized. This allows the quantum-to-classical transition to be described from individual measurement records, complementing the ensemble description from density matrices. We further show that the same scattering that decoheres a trajectory heats it, tying decoherence and measurement back-action together. This bounds how redundantly an individual classical trajectory can be recorded before back-action randomises it into Brownian motion. For a trapped particle, the ceiling is fixed by the resolution measured in units of the zero-point motion. It is not restrictive for macroscopic systems; it collapses to a single record where the semiclassical description of a trajectory fails, delimiting the regime in which objective classical trajectories exist. The deterministic-to-Brownian crossover is accessible in levitated optomechanics.
The path integral approach to quantum mechanics requires a substantial generalisation to describe the dynamics of systems confined to bounded domains. Nonlocal boundary conditions can be introduced in Feynman's approach by means of boundary amplitude distributions and complex phases to describe the quantum dynamics in terms of the classical trajectories. The different prescriptions involve only trajectories reaching the boundary and correspond to different choices of boundary conditions of selfadjoint extensions of the Hamiltonian. One dimensional particle dynamics is analysed in detail.
A path , in general, is defined by a determinate trajectory in time, from an initial to a final point. The classical trajectory is only one of the possible trajectories, and in quantum mechanics all the possible paths between the initial and final point come into play. Recall that the probability amplitude is a complex number that is assigned to each determinate path. Indeterminate paths are defined as a collection of determinate paths that are experimentally indistinguishable . In the Dirac–Feynman approach, the inherent indeterminacy of the quantum entity is realized by the degree of freedom – in undergoing time evolution – “taking” indeterminate paths [Baaquie (2013e)]. For a quantum degree of freedom evolving from an observed initial state to the observed final state – and with no other observations made – the Feynman path integral is a mathematical construction that computes the probability amplitudes by summing over all the allowed determinate paths of the degree of freedom – discussed in Feynman and Hibbs (1965), Zinn-Justin (1993), Zinn-Justin (2005) and Baaquie (2013e). Probability amplitude and time evolution Recall that the description of a quantum system, at a particular instant,isgiven by its state vector, namely |ψ>. To avoid confusion with the concept of a state vector, the term probability amplitude is used for describing a quantum entity undergoing transitions in time.
The method, described in the paper, incorporates ideas of the Bohmian formulation of quantum mechanics into a trajectory approach designed for systems comprised of light (quantum) and heavy (nearly classical) particles. The goal is to treat all degrees of freedom on the same footing but, for practical reasons, to include the quantum-mechanical effects into dynamics for just the light particles. The total wavefunction, taken as a product of slow and fast components representing the heavy and light particles respectively is represented in terms of trajectories. The fast component depends on the trajectory-guided configurations of the heavy particles. The initial conditions for the trajectories are defined by the full-dimensional initial wavefunction according to Bohm's prescription of associating the trajectory momentum with the gradient of the wavefunction phase. The time-dependent Schrödinger equation is solved for the quantum degrees of freedom using an ensemble of the quantum trajectories (or other time-propagation method) for each guiding trajectory of the classical subspace. Neglect of the quantum force acting on the heavy particles allows decoupling of the quantum calculations associated with different guiding trajectories. The approach allows reconstruction of the full-dimensional wavefunction and conserves the total wavefunction energy as illustrated for the vibrationally non-adiabatic model.