Recommendations for Velocity Adjustment in Surface Hopping - Archive ouverte HAL Accéder directement au contenu
Article Dans Une Revue Journal of Chemical Theory and Computation Année : 2024

Recommendations for Velocity Adjustment in Surface Hopping

Josene M Toldo
Rafael S Mattos
Max Pinheiro
Saikat Mukherjee

Résumé

This study investigates velocity adjustment directions after hoppings in surface hopping dynamics. Using fulvene and a protonated Schiff base (PSB4) as case studies, we investigate the population decay and reaction yields of different sets of dynamics with the velocity adjusted either in the nonadiabatic coupling, gradient difference, or momentum directions. For the latter, besides the conventional algorithm, we investigated the performance of a reduced kinetic energy reservoir approach recently proposed. Our evaluation also considered velocity adjustment in the directions of approximate nonadiabatic coupling vectors. While results for fulvene are susceptible to the adjustment approach, PSB4 is not. We correlated this dependence to the topography near the conical intersections. When nonadiabatic coupling vectors are unavailable, the gradient difference direction is the best adjustment option. If the gradient difference is also unavailable, a semiempirical vector direction or the momentum direction with a reduced kinetic energy reservoir becomes an excellent option to prevent an artificial excess of back hoppings. The precise velocity adjustment direction is less crucial for describing the nonadiabatic dynamics than the kinetic energy reservoir's size.
Fichier sous embargo
Fichier sous embargo
0 2 14
Année Mois Jours
Avant la publication
vendredi 12 juillet 2024
Fichier sous embargo
vendredi 12 juillet 2024
Connectez-vous pour demander l'accès au fichier

Dates et versions

hal-04389834 , version 1 (12-01-2024)

Identifiants

Citer

Josene M Toldo, Rafael S Mattos, Max Pinheiro, Saikat Mukherjee, Mario Barbatti. Recommendations for Velocity Adjustment in Surface Hopping. Journal of Chemical Theory and Computation, In press, ⟨10.1021/acs.jctc.3c01159⟩. ⟨hal-04389834⟩
31 Consultations
1 Téléchargements

Altmetric

Partager

Gmail Facebook X LinkedIn More