Nonadiabatic Field on Quantum Phase Space: A Century after Ehrenfest

Abstract

Nonadiabatic transition dynamics lies at the core of many electron/hole transfer, photoactivated, and vacuum field-coupled processes. About a century after Ehrenfest proposed "Phasenraum" and the Ehrenfest theorem, we report a conceptually novel trajectory-based nonadiabatic dynamics approach, nonadiabatic field (NaF), based on a generalized exact coordinate-momentum phase space formulation of quantum mechanics. It does not employ the conventional Born-Oppenheimer or Ehrenfest trajectory in the nonadiabatic coupling region. Instead, in NaF the equations of motion of the independent trajectory involve a nonadiabatic nuclear force term in addition to an adiabatic nuclear force term of a single electronic state. A few benchmark tests for gas phase and condensed phase systems indicate that NaF offers a practical tool to capture the correct correlation of electronic and nuclear dynamics for processes where the states remain coupled all the time as well as for the asymptotic region where the coupling of electronic states vanishes.

References in corpus (18)

• A general method to describe intersystem crossing dynamics in trajectory surface hopping
• Exact quantum master equation via the calculus on path integrals
• Coupled Cluster Theory for Molecular Polaritons: Changing Ground and Excited States
• A hybrid stochastic hierarchy equations of motion approach to treat the low temperature dynamics of non-Markovian open quantum systems
• Circuit QED using a semiconductor double quantum dot
• A Unified Theoretical Framework for Mapping Models for the Multi-State Hamiltonian
• Capturing Vacuum Fluctuations and Photon Correlations in Cavity Quantum Electrodynamics with Multi-Trajectory Ehrenfest Dynamics
• Unified Formulation of Phase Space Mapping Approaches for Nonadiabatic Quantum Dynamics
• Benchmarking Semiclassical and Perturbative Methods for Real-time Simulations of Cavity-Bound Emission and Interference
• Quasiclassical Modeling of Cavity Quantum Electrodynamics
• New Phase Space Formulations and Quantum Dynamics Approaches
• Negative Zero-Point-Energy Parameter in the Meyer-Miller Mapping Model for Nonadiabatic Dynamics
• The hierarchical and perturbative forms of stochastic Schrödinger equations and their applications to carrier dynamics in organic materials
• Commutator Matrix in Phase Space Mapping Models for Nonadiabatic Quantum Dynamics
• Path Integral Molecular Dynamics for Exact Quantum Statistics of Multi-Electronic-State Systems
• Collective Multi-mode Vacuum Rabi Splitting
• Isomorphism between the multi-state Hamiltonian and the second-quantized many-electron Hamiltonian with only 1-electron interactions
• Generalized Discrete Truncated Wigner Approximation for Nonadiabtic Quantum-Classical Dynamics

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• A Novel Class of Phase Space Representations for the Exact Population Dynamics of Two-State Quantum Systems and the Relation to Triangle Window Functions
• Fermi's golden rule rate expression for transitions due to nonadiabatic derivative couplings in the adiabatic basis
• Twin-Space Representation of Classical Mapping Model in the Constraint Phase Space Representation: Numerically Exact Approach to Open Quantum Systems
• Ehrenfest dynamics accelerated with SPEED
• Geometric Phase Effect in Thermodynamic Properties and in the Imaginary-Time Multi-Electronic-State Path Integral Formulation