Issue 3, 2022

Resolving competing conical intersection pathways: time-resolved X-ray absorption spectroscopy of trans-1,3-butadiene

Abstract

Time-resolved X-ray absorption spectroscopy is emerging as a uniquely powerful tool to probe coupled electronic-nuclear dynamics in photo-excited molecules. Theoretical studies to date have established that time-resolved X-ray absorption spectroscopy is an atom-specific probe of excited-state wave packet passage through a seam of conical intersections (CIs). However, in many molecular systems, there are competing dynamical pathways involving CIs of different electronic and nuclear character. Discerning these pathways remains an important challenge. Here, we demonstrate that time-resolved X-ray absorption spectroscopy (TRXAS) has the potential to resolve competing channels in excited-state non-adiabatic dynamics. Using the example of 1,3-butadiene, we show how TRXAS discerns the different electronic structures associated with passage through multiple conical intersections. trans-1,3-Butadiene exhibits a branching between polarized and radicaloid pathways associated with ethylenic “twisted-pyramidalized” and excited-state cistrans isomerization dynamics, respectively. The differing electronic structures along these pathways give rise to different XAS signals, indicating the possibility of resolving them. Furthermore, this indicates that XAS, and other core-level spectroscopic techniques, offer the appealing prospect of directly probing the effects of selective chemical substitution and its ability to affect chemical control over excited-state molecular dynamics.

Graphical abstract: Resolving competing conical intersection pathways: time-resolved X-ray absorption spectroscopy of trans-1,3-butadiene

Supplementary files

Article information

Article type
Paper
Submitted
07 nov 2021
Accepted
13 dec 2021
First published
13 dec 2021

Phys. Chem. Chem. Phys., 2022,24, 1345-1354

Resolving competing conical intersection pathways: time-resolved X-ray absorption spectroscopy of trans-1,3-butadiene

I. Seidu, S. P. Neville, R. J. MacDonell and M. S. Schuurman, Phys. Chem. Chem. Phys., 2022, 24, 1345 DOI: 10.1039/D1CP05085K

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