Abstract
Photoelectron circular dichroism (PECD), the forward-backward asymmetry of the photoelectron angular distribution when ionizing randomly oriented chiral molecules with circularly polarized light, is an established method to investigate chiral properties of molecules in their electronic ground state. Here, we develop a computational strategy for predicting time-resolved PECD (TRPECD) of chemical reactions and demonstrate the method on the photodissociation of 1-iodo-2-methylbutane. Our approach combines multi-configurational quantum-chemical calculations of the relevant potential-energy surfaces of the neutral and singly ionized molecule with ab initio molecular-dynamics (AIMD) calculations. The PECD parameters along the AIMD trajectories are calculated with the aid of electron-molecule scattering calculations based on the Schwinger variational principle implemented in ePolyScat. Our calculations have been performed for two probe wavelengths (133 and 160 nm) accessible through low-order harmonic generation in gases. Our results show that the TRPECD is a highly sensitive probe of photochemical reaction dynamics. Most interestingly, the TRPECD is found to change sign multiple times along the photodissociation coordinate, in agreement with recent experiments on CHBrFI [Svoboda et al., "Femtosecond photoelectron circular dichroism of chemical reactions," Sci. Adv. 8, eabq2811 (2022)]. The computational protocol introduced in the present work is general and readily applicable to other chiral photochemical processes.
Talk to us
Join us for a 30 min session where you can share your feedback and ask us any queries you have
Disclaimer: All third-party content on this website/platform is and will remain the property of their respective owners and is provided on "as is" basis without any warranties, express or implied. Use of third-party content does not indicate any affiliation, sponsorship with or endorsement by them. Any references to third-party content is to identify the corresponding services and shall be considered fair use under The CopyrightLaw.