Tracking nuclear wave packets in excited-state reactions via quantum mechanics/molecular dynamics simulations

Abstract

Nuclear wave packets (NWPs) in electronically excited states generated by ultrashort laser pulses can persist through photochemical processes and be detected in the product state. The NWPs that are coupled with the reaction dynamics undergo changes during the process and provide crucial insights into potential energy surfaces and molecular reaction dynamics. We present a computational method to calculate NWPs in the products of ultrafast photochemical processes by projecting nuclear displacements, obtained via Born–Oppenheimer molecular dynamics simulations, onto the normal modes of the reaction product state. Applying this approach to the excited-state intramolecular proton transfer reaction of 10-hydroxybenzo[h]quinoline, we successfully reproduced the experimentally observed NWPs in the reaction product, which were measured by time-resolved fluorescence of the product state with high fidelity. This significant achievement enables the analysis of individual normal mode motions following photoexcitation in chemical and physical processes. By integrating highly time-resolved spectroscopy with computational modeling, this method provides an effective approach to investigate the excited-state potential energy surfaces and the associated nuclear dynamics.