Nonadiabatic Field: A Conceptually Novel Approach for Nonadiabatic Quantum Molecular Dynamics

Abstract

Reliable trajectory-based nonadiabatic quantum dynamics methods at the atomic level are critical for understanding many important processes in real systems. The paper reports latest progress of nonadiabatic field (NaF), a conceptually novel approach for nonadiabatic quantum dynamics with independent trajectories. Substantially different from the mainstreams of Ehrenfest-like dynamics and surface hopping methods, the nuclear force in NaF involves the nonadiabatic force arising from the nonadiabatic coupling between different electronic states, in addition to the adiabatic force contributed by a single adiabatic electronic state. NaF is capable of faithfully describing the interplay between electronic and nuclear motion in a broad regime, which covers where the relevant electronic states keep coupled in a wide range or all the time and where the bifurcation characteristic of nuclear motion is essential. NaF is derived from the exact generalized phase space formulation with coordinate-momentum variables, where constraint phase space (CPS) is employed for discrete electronic-state degrees of freedom. We propose efficient integrators for the equations of motion of NaF in both adiabatic and diabatic representations. Since the formalism in the CPS formulation is not unique, NaF can in principle be implemented with various phase space representations of the time correlation function (TCF) for the time-dependent property. They are applied to a suite of representative gas-phase and condensed-phase benchmark models where numerically exact results are available for comparison. It is shown that NaF is relatively insensitive to the phase space representation of the electronic TCF and will be a potential tool for practical and reliable simulations of the quantum mechanical behavior of both electronic and nuclear dynamics of nonadiabatic transition processes in real systems.

References in corpus (84)

• The density-matrix renormalization group in the age of matrix product states
• Efficient simulation of one-dimensional quantum many-body systems
• Matrix Product Density Operators: Simulation of finite-T and dissipative systems
• Unifying time evolution and optimization with matrix product states
• Mixed-state dynamics in one-dimensional quantum lattice systems: a time-dependent superoperator renormalization algorithm
• Atoms and Molecules in Cavities: From Weak to Strong Coupling in QED Chemistry
• Phase space representation of quantum dynamics
• Efficient simulation of strong system-environment interactions
• Exact factorization of the time-dependent electron-nuclear wavefunction
• A general method to describe intersystem crossing dynamics in trajectory surface hopping
• Exact quantum master equation via the calculus on path integrals
• Correlated electron-nuclear dynamics: Exact factorization of the molecular wavefunction
• Delocalized excitons in natural light harvesting complexes
• Cavity Born-Oppenheimer Approximation for Correlated Electron-Nuclear-Photon Systems
• Time-dependent density functional theory for many-electron systems interacting with cavity photons
• Ab-initio non-relativistic quantum electrodynamics: Bridging quantum chemistry and quantum optics from weak to strong coupling
• Breakdown of gauge invariance in ultrastrong-coupling cavity QED
• Time integration of tensor trains
• Analytical derivative coupling for multistate CASPT2 theory
• Kohn-Sham Approach to Quantum Electrodynamical Density Functional Theory: Exact Time-Dependent Effective Potentials in Real Space
• Optimized Effective Potential for Quantum Electrodynamical Time-Dependent Density Functional Theory
• Quantum phase transitions in the sub-ohmic spin-boson model: Failure of the quantum-classical mapping
• Cavity molecular dynamics simulations of liquid water under vibrational ultrastrong coupling
• Ab-initio Optimized Effective Potentials for Real Molecules in Optical Cavities: Photon Contributions to the Molecular Ground state
• A hybrid stochastic hierarchy equations of motion approach to treat the low temperature dynamics of non-Markovian open quantum systems
• Wigner Functions for Arbitrary Quantum Systems
• Generalized spin mapping for quantum-classical dynamics
• Large-scale quantum-dynamics with matrix product states
• Spin-mapping approach for nonadiabatic molecular dynamics
• A mapping approach to surface hopping
• A Unified Theoretical Framework for Mapping Models for the Multi-State Hamiltonian
• Exact quantum statistics for electronically nonadiabatic systems using continuous path variables
• Time-step targeting time-dependent and dynamical density matrix renormalization group algorithms with ab initio Hamiltonians
• Surface hopping from the perspective of quantum-classical Liouville dynamics
• Capturing Vacuum Fluctuations and Photon Correlations in Cavity Quantum Electrodynamics with Multi-Trajectory Ehrenfest Dynamics
• On the identity of the identity operator in nonadiabatic linearized semiclassical 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
• A multi-state mapping approach to surface hopping
• Improved population operators for multi-state nonadiabatic dynamics with the mixed quantum-classical mapping approach
• Mixed quantum-classical dynamics on the exact time-dependent potential energy surface: A fresh look at non-adiabatic processes
• On the accuracy of surface hopping dynamics in condensed phase non-adiabatic problems
• Finite Temperature TD-DMRG for the Carrier Mobility of Organic Semiconductors
• Heat transfer in the spin-boson model: A comparative study in the incoherent tunneling regime
• Mixed Quantum-Classical Electrodynamics: Understanding Spontaneous Decay and Zero Point Energy
• Quasiclassical Modeling of Cavity Quantum Electrodynamics
• Ehrenfest+R Dynamics I: A Mixed Quantum-Classical Electrodynamics Simulation of Spontaneous Emission
• New Phase Space Formulations and Quantum Dynamics Approaches
• A general approach to quantum mechanics as a statistical theory
• Deriving the exact nonadiabatic quantum propagator in the mapping variable representation
• Tensor-Train Thermo-Field Memory Kernels for Generalized Quantum Master Equations
• Critical role of quantum dynamical effects in the Raman spectroscopy of liquid water
• 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
• Nonadiabatic Field on Quantum Phase Space: A Century after Ehrenfest
• Quantum mechanics of open systems: Dissipaton theories
• SU(N)-symmetric quasi-probability distribution functions
• Performance Evaluation of the Symmetrical Quasi-Classical Dynamics Method based on Meyer-Miller Mapping Hamiltonian in the Treatment of Site-Exciton Models
• Path Integral Molecular Dynamics for Exact Quantum Statistics of Multi-Electronic-State Systems
• Equilibrium and transient thermodynamics: A unified dissipaton-space approach
• A Comparison of Different Classical, Semiclassical and Quantum Treatments of Light-Matter Interactions: Understanding Energy Conservation
• Nonadiabatic Field with Triangle Window Functions on Quantum Phase Space
• Isomorphism between the multi-state Hamiltonian and the second-quantized many-electron Hamiltonian with only 1-electron interactions
• Tangent space formulation of the Multi-Configuration Time-Dependent Hartree equations of motion: The projector-splitting algorithm revisited
• A Linearized Semiclassical dynamics study of the multi-quantum vibrational relaxation of NO scattering from a Au(111) Surface
• Multi-State Trajectory Approach to Non-Adiabatic Dynamics: General Formalism and the Active State Trajectory Approximation
• Generalized Discrete Truncated Wigner Approximation for Nonadiabtic Quantum-Classical Dynamics
• A Necessary Trade-off for Semiclassical Electrodynamics: Accurate Short-Range Coulomb Interactions versus the Enforcement of Causality?
• Predictive Semiclassical Model for Coherent and Incoherent Emission in the Strong Field Regime: The Mollow Triplet Revisited
• A Langevin canonical approach to the dynamics of two level systems. I. Populations and coherences
• Classical and quantum light-induced non-adiabaticity in molecular systems
• Semiclassical Nonadiabatic Molecular Dynamics Using Linearized Pair-Density Functional Theory
• The symmetric quasi-classical model using on-the-fly time-dependent density functional theory within the Tamm-Dancoff approximation
• Initial Sampling in Symmetrical Quasiclassical Dynamics Based on Li-Miller Mapping Hamiltonian
• A Novel Class of Phase Space Representations for the Exact Population Dynamics of Two-State Quantum Systems and the Relation to Triangle Window Functions
• Dissipative and stochastic geometric phase of a qubit within a canonical Langevin framework
• Understanding the Nature of Mean-Field Semiclassical Light-Matter Dynamics: An Investigation of Energy Transfer, Electron-Electron Correlations, External Driving and Long-Time Detailed Balance
• A Langevin canonical approach to the dynamics of chiral two level systems. Thermal averages and heat capacity
• Phase space quantum-classical hybrid model
• Numerical variational simulations of quantum phase transitions in the sub-Ohmic spin-boson model with multiple polaron ansatz
• Twin-Space Representation of Classical Mapping Model in the Constraint Phase Space Representation: Numerically Exact Approach to Open Quantum Systems
• Comment on "Unified framework for open quantum dynamics with memory"
• Constraint Phase Space Formulations for Finite-State Quantum Systems: The Relation between Commutator Variables and Complex Stiefel Manifolds

Cited by in corpus (6)

• A Descriptor Is All You Need: Accurate Machine Learning of Nonadiabatic Coupling Vectors
• Twin-Space Representation of Classical Mapping Model in the Constraint Phase Space Representation: Numerically Exact Approach to Open Quantum Systems
• Geometric Phase Effect in Thermodynamic Properties and in the Imaginary-Time Multi-Electronic-State Path Integral Formulation
• Exponential convergence of the local diabatic representation for nonadiabatic models
• Unifying Decoherence and Phase Evolution in Mixed Quantum-Classical Dynamics through Exact Factorization
• Path-Integral Approach to Quantum Acoustics