Spectral Signatures of Ultrafast Excited-State Intramolecular Proton Transfer from Computational Multi-edge Transient X-ray Absorption Spectroscopy

Excited-state intramolecular proton transfer (ESIPT) is a fundamental chemical process with several applications. Ultrafast ESIPT involves coupled electronic and atomic motions and has been primarily studied using femtosecond optical spectroscopy. X-ray spectroscopy is particularly useful because it is element-specific and enables direct, individual probes of the proton-donating and -accepting atoms. Herein, we report a computational study to resolve the ESIPT in 10-hydroxybenzo[h]quinoline (HBQ), an intramolecularly hydrogen bonded compound. We use linear-response time-dependent density functional theory (LR-TDDFT) combined with ab initio molecular dynamics (AIMD) and time-resolved X-ray absorption spectroscopy (XAS) computations to track the ultrafast excited-state dynamics. Our results reveal clear X-ray spectral signatures of coupled electronic and atomic motions during and following ESIPT at the oxygen and nitrogen K-edge, paving the way for future experiments at X-ray free electron lasers.