Mapping State Space to Quasiclassical Trajectory Dynamics in Coherence-Controlled Nonadiabatic Simulations for...

Area of Science:

• * Quantum chemistry
• * Molecular dynamics
• * Physical chemistry

Background:

• * Nonadiabatic dynamics are crucial for understanding chemical reactions and energy transfer.
• * Existing methods often struggle with accuracy and efficiency in high-dimensional systems.
• * The coherence controlled (CC) approach offers a novel framework for these simulations.

Purpose of the Study:

• * To elaborate the state-space decomposition and mapping in the CC approach for general high-dimensional systems.
• * To demonstrate the feasibility and performance of the CC approach for condensed phase nonadiabatic molecular dynamics.
• * To assess the accuracy and efficiency of the CC method against benchmark calculations.

Main Methods:

• * Development and generalization of the state-space decomposition scheme for the CC approach.
• * Application of the CC formalism using an ensemble of trajectories in the active state space.
• * Implementation and testing on benchmark problems: spin-boson model and photosynthetic energy transfer.

Main Results:

• * The CC approach successfully describes nonadiabatic molecular dynamics in condensed phase systems.
• * Results show good agreement with exact and benchmark calculations.
• * The method approximately satisfies detailed balance and demonstrates efficient simulation capabilities.

Conclusions:

• * The elaborated CC approach provides a robust and accurate framework for high-dimensional nonadiabatic dynamics.
• * The CC method is efficient for simulating condensed phase systems at reasonable accuracy.
• * This work validates the CC approach for complex molecular dynamics problems.