Influence of Mode-Specific Excitation on the Nonadiabatic Dynamics of Methyl Nitrate (CH₃ONO₂)

Theimpact of mode-specific vibrational excitations oninitial-preparationconditions was studied by examining the excited-state population decayrates in the nonadiabatic dynamics of methyl nitrate (CH3ONO2). In particular, exciting a few specific modes byadding a single quantum of energy clearly decelerated the nonadiabaticdynamics population decay rates. The underlying reason for this slowerpopulation decay was explained by analyzing the profiles of the excited-statepotential energy surfaces in the Franck-Condon regions andthe topology of the S-1/S-0 conical intersection.This study not only provides physical insights into the key mechanismscontrolling nonadiabatic dynamics but also shows the possibility ofcontrolling nonadiabatic dynamics via mode-specific vibrational excitations.