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

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. Based on 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 CH${}_3$I molecule that the observed signatures allow us to map the time-dependent dynamics of ultrafast photo-induced bond breaking with unprecedented details.

arXiv commentThis document is the unedited Author's version of a Submitted Work that was subsequently accepted for publication in The Journal of Physical Chemistry Letters, copyright (c) American Chemical Society after peer review. To access the final edited and published work see https://pubs.acs.org/articlesonrequest/AOR-Cvsg7nKYk4KJtQFRUb6I

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• 0.5 keV soft X-ray attosecond continua
• Probing ultrafast ππ*/nπ* internal conversion in organic chromophores via K-edge resonant absorption
• Efficient electronic structure calculation for molecular ionization dynamics at high x-ray intensity
• Time-resolved inner-shell photoelectron spectroscopy: from a bound molecule to an isolated atom
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