Spectroscopic Signature of Chemical Bond Dissociation Revealed by Calculated Core-Electron Spectra

J Phys Chem Lett. 2019 Nov 7;10(21):6536-6544. doi: 10.1021/acs.jpclett.9b02370. Epub 2019 Oct 14.

Abstract

The advent of ultrashort soft X-ray pulse sources permits the use of established gas-phase spectroscopy methods to investigate ultrafast photochemistry in isolated molecules with element and site specificity. In the present study, we simulate excited-state wavepacket dynamics of a prototypical process, the ultrafast photodissociation of methyl iodide. Using the simulation, we calculate time-dependent excited-state carbon edge photoelectron and Auger electron spectra. We observe distinct signatures in both types of spectra and show their direct connection to C-I bond dissociation and charge rearrangement processes in the molecule. We demonstrate at the CH3I molecule that the observed signatures allow us to map the time-dependent dynamics of ultrafast photoinduced bond breaking with unprecedented detail.