Path Integral Molecular Dynamics for Exact Quantum Statistics of Multi-Electronic-State Systems
arXiv:1710.04126 · doi:10.1063/1.5005059
Abstract
An exact approach to compute physical properties for general multi-electronic-state (MES) systems in thermal equilibrium is presented. The approach is extended from our recent progress on path integral molecular dynamics (PIMD) [J. Chem. Phys. 145, 024103 (2016); 147, 034109 (2017)] for quantum statistical mechanics when a single potential energy surface is involved. We first define an effective potential function that is numerically favorable for MES-PIMD, and then derive corresponding estimators in MES-PIMD for evaluating various physical properties. Its application to several representative one-dimensional and multi-dimensional models demonstrates that MES-PIMD in principle offers a practical tool in either of the diabatic and adiabatic representations for studying exact quantum statistics of complex/large MES systems when the Born-Oppenheimer approximation, Condon approximation, and harmonic bath approximation are broken.
References in corpus (16)
- Efficient stochastic thermostatting of path integral molecular dynamics
- Worm Algorithm for Continuous-space Path Integral Monte Carlo Simulations
- Reduced hierarchical equations of motion in real and imaginary time: Correlated initial states and thermodynamic quantities
- Accelerating the convergence of path integral dynamics with a generalized Langevin equation
- Rational Construction of Stochastic Numerical Methods for Molecular Sampling
- A simple and accurate algorithm for path integral molecular dynamics with the Langevin thermostat
- An exact equilibrium reduced density matrix formulation I: The influence of noise, disorder, and temperature on localization in excitonic systems
- A unified thermostat scheme for efficient configurational sampling for classical/quantum canonical ensembles via molecular dynamics
- Numerically exact, time-dependent treatment of vibrationally coupled electron transport in single-molecule junctions
- A Unified Theoretical Framework for Mapping Models for the Multi-State Hamiltonian
- Exact quantum statistics for electronically nonadiabatic systems using continuous path variables
- Numerically exact, time-dependent study of correlated electron transport in model molecular junctions
- Non-oscillatory flux correlation functions for efficient nonadiabatic rate theory
- Path integral molecular dynamics with surface hopping for thermal equilibrium sampling of nonadiabatic systems
- Isomorphism between the multi-state Hamiltonian and the second-quantized many-electron Hamiltonian with only 1-electron interactions
- The Rigorous Stochastic Matrix Multiplication Scheme for the Calculations of Reduced Equilibrium Density Matrices of Open Multilevel Quantum Systems
Cited by in corpus (9)
- Unified Formulation of Phase Space Mapping Approaches for Nonadiabatic Quantum Dynamics
- Critical role of quantum dynamical effects in the Raman spectroscopy of liquid water
- Nonadiabatic Field on Quantum Phase Space: A Century after Ehrenfest
- Nonadiabatic Field: A Conceptually Novel Approach for Nonadiabatic Quantum Molecular Dynamics
- Continuum limit and preconditioned Langevin sampling of the path integral molecular dynamics
- The Bayesian Inversion Problem for Thermal Average Sampling of 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
- Path-Integral Approach to Quantum Acoustics