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Influence of Vibrational Excitation and Nuclear Dynamics in Multiphoton Photoelectron Circular Dichroism of Fenchone

Singh, Dhirendra P.; Thompson, James O. F.; Reid, Katharine L.; Powis, Ivan

Influence of Vibrational Excitation and Nuclear Dynamics in Multiphoton Photoelectron Circular Dichroism of Fenchone Thumbnail


Authors

Dhirendra P. Singh

James O. F. Thompson

Ivan Powis



Abstract

We report photoelectron circular dichroism of S-(+)-fenchone enantiomers recorded with state-state vibrational level resolution using picosecond laser (2 + 1) resonance enhanced multiphoton ionization via 3s and 3p Rydberg intermediate states. The 3p state decays to the 3s state on a picosecond time scale so that, above the 3p Rydberg excitation threshold, ionization of vibrationally hot 3s states competes with direct 3p-1 ionization. Complex vibronic dynamics of the 3p → 3s internal conversion weaken the Rydberg Δv = 0 propensity rule in both the 3p-1 and 3s-1 ionization channels. Large variations of the forward-backward chiral asymmetry factors are observed between the Δv = 0 and Δv > 0 vibrational transitions, including dramatic swings from up to ±17%. Such changes of sign indicate complete reversal of the preferred direction for photoelectron emission in the laboratory frame, associated with vibrational motion. These asymmetry switches easily exceed the amplitude and frequency of such vibrationally induced flips previously observed in single photon ionization.

Journal Article Type Article
Acceptance Date Nov 9, 2021
Online Publication Date Nov 18, 2021
Publication Date Nov 25, 2021
Deposit Date Nov 25, 2021
Publicly Available Date Nov 19, 2022
Journal Journal of Physical Chemistry Letters
Print ISSN 1948-7185
Electronic ISSN 1948-7185
Publisher American Chemical Society (ACS)
Peer Reviewed Peer Reviewed
Volume 12
Issue 46
Pages 11438-11443
DOI https://doi.org/10.1021/acs.jpclett.1c03231
Keywords General Materials Science; Physical and Theoretical Chemistry
Public URL https://nottingham-repository.worktribe.com/output/6788395
Publisher URL https://pubs.acs.org/doi/10.1021/acs.jpclett.1c03231
Additional Information This document is the Accepted Manuscript version of a Published Work that appeared in final form in Journal of Physical Chemistry Letters. copyright © American Chemical Society after peer review and technical editing by the publisher. To access the final edited and published work see https://pubs.acs.org/doi/10.1021/acs.jpclett.1c03231.

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