A Simple Solution to the Trivial Crossing Problem in Surface Hopping.

Area of Science:

• Computational Chemistry
• Quantum Dynamics
• Materials Science

Background:

• Surface hopping simulations are crucial for studying molecular dynamics.
• The trivial crossing problem hinders accuracy in complex systems with dense potential energy surfaces.

Purpose of the Study:

• To address the trivial crossing problem in surface hopping methods.
• To develop a more efficient and accurate simulation technique for nanoscale systems.

Main Methods:

• Introduction of a self-consistency test into the fewest switches surface hopping (FSSH) algorithm.
• Development of the self-consistent fewest switches surface hopping (SC-FSSH) approach.
• Application to the Holstein Hamiltonian to analyze electron population dynamics.

Main Results:

• SC-FSSH effectively resolves the trivial crossing problem.
• A 10,000-fold reduction in simulation time was achieved for a five-state system.
• SC-FSSH maintains the accuracy of the original FSSH method.

Conclusions:

• SC-FSSH offers a robust and efficient solution for surface hopping simulations.
• The method's simplicity and reliability expand the applicability of surface hopping techniques.
• Enables more accessible and faster computational studies of supramolecular and nanoscale phenomena.