On the electronic path integral normal modes of the Meyer-Miller-Stock-Thoss representation of nonadiabatic dynamics
arXiv:2508.14775 · doi:10.1063/5.0297571
Abstract
Accurate and efficient simulation of nonadiabatic dynamics is highly desirable for understanding charge and energy transfer in complex systems. A key criterion for obtaining an accurate method is conservation of the Quantum Boltzmann Distribution (QBD). For a single surface, Matsubara dynamics is known to conserve the QBD, as a consequence of truncating the dynamics in the higher normal modes of the imaginary-time path integral. Recently, a nonadiabatic Matsubara (NA-Mats) dynamics has been proposed (J. Chem. Phys., 2021, 154, 124124) which truncates in the normal modes of the nuclear variables but not in the electronic variables, which are described with the Meyer-Miller-Stock-Thoss (MMST) representation. Surprisingly, this NA-Mats method does not appear to conserve the QBD for a general system. This poses the question of the effect of truncating the higher path integral normal modes of the electronic variables in the MMST representation. In this article, we present what we believe is the first study of electronic normal modes of the MMST representation. We find that observables are not usually a function of a finite number of normal modes and that the higher normal modes are not constrained by the distribution, unlike in conventional nuclear normal modes. Furthermore, truncating the dynamics in MMST normal modes leads to inaccurate correlation functions and while the QBD appears conserved for an ensemble of trajectories, it is not for a single trajectory. Overall, this suggests that MMST path integral normal modes are not optimal for obtaining an accurate, QBD conserving nonadiabatic dynamics method.
arXiv comment14 pages, 7 figures, submitted to JCP, SI available as ancillary file
References in corpus (27)
- Efficient stochastic thermostatting of path integral molecular dynamics
- How to remove the spurious resonances from ring polymer molecular dynamics
- Mapping Variable Ring Polymer Molecular Dynamics: A Path-Integral Based Method for Nonadiabatic Processes
- Boltzmann-conserving classical dynamics in quantum time-correlation functions: Matsubara dynamics
- Mapping quantum-classical Liouville equation: projectors and trajectories
- Generalized spin mapping for quantum-classical dynamics
- Derivation of a true (t->0+) quantum transition-state theory. Part I: Uniqueness and equivalence to ring-polymer molecular dynamics transition-state-theory
- Spin-mapping approach for nonadiabatic molecular dynamics
- Relation of centroid molecular dynamics and ring-polymer molecular dynamics to exact quantum dynamics
- A mapping approach to surface hopping
- Surface hopping from the perspective of quantum-classical Liouville dynamics
- Improved population operators for multi-state nonadiabatic dynamics with the mixed quantum-classical mapping approach
- An analysis of nonadiabatic ring-polymer molecular dynamics and its application to vibronic spectra
- Derivation of a true (t->0+) quantum transition-state theory. II. Recovery of the exact quantum rate in the absence of recrossing
- A partially linearized spin-mapping approach for nonadiabatic dynamics. I. Derivation of the theory
- Nonadiabatic semiclassical dynamics in the mixed quantum-classical initial value representation
- Deriving the exact nonadiabatic quantum propagator in the mapping variable representation
- On the uniqueness of t->0+ quantum transition-state theory
- Should Thermostatted Ring Polymer Molecular Dynamics be used to calculate thermal reaction rates?
- How to obtain thermostatted ring polymer molecular dynamics from exact quantum dynamics and when to use it
- Exciton dynamics from the mapping approach to surface hopping: Comparison with Förster and Redfield theories
- Quantum entanglement from classical trajectories
- On detailed balance in nonadiabatic dynamics: From spin spheres to equilibrium ellipsoids
- An alternative derivation of ring-polymer molecular dynamics transition-state theory
- Non-Adiabatic Ring Polymer Molecular Dynamics with Spin Mapping Variables
- Which Algorithm Best Propagates the Meyer-Miller-Stock-Thoss Mapping Hamiltonian for Non-Adiabatic Dynamics?
- Time-reversible implementation of MASH for efficient nonadiabatic molecular dynamics