Non-Born-Oppenheimer Molecular Dynamics Observed by Coherent Nuclear Wave Packets

Abstract

The reaction dynamics of a photochemical reaction is typically described by reaction coordinates based on the Born-Oppenheimer (BO) approximation. A strong interaction between electrons and nuclei, conventionally occurring at conical intersections, however, breaks the BO approximation and has major consequences for the efficiency of a photochemical reaction. Despite its importance, related studies into the non-BO dynamics are scarce. Here, we investigate the non-BO dynamics of excited-state intramolecular proton transfer (ESIPT) occurring in 10-hydroxybenzo[h]quinoline (HBQ). Two coherent vibrational modes at 237 and 794 cm(-1) representing molecular dynamics on a diabatic surface in HBQ are identified by a wave packet analysis based on a transient absorption measurement with a time resolution of 11 fs and with a density functional theory-based model calculation. It is also revealed that the strong Coulomb field effect in HBQ leads to the completion of ESIPT within about two cycles of the OH stretching mode. The work paves the way for time-domain studies of molecular dynamics beyond the BO approximation in other photochemical reactions.