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Vibrationally induced inversion of photoelectron forward-backward asymmetry in chiral molecule photoionization by circularly polarized light

Garcia, Gustavo A.; Nahon, Laurent; Daly, Steven; Powis, Ivan

Vibrationally induced inversion of photoelectron forward-backward asymmetry in chiral molecule photoionization by circularly polarized light Thumbnail


Authors

Gustavo A. Garcia

Laurent Nahon

Steven Daly

Ivan Powis



Abstract

Electron–nuclei coupling accompanying excitation and relaxation processes is a fascinating phenomenon in molecular dynamics. A striking and unexpected example of such coupling is presented here in the context of photoelectron circular dichroism measurements on randomly oriented, chiral methyloxirane molecules, unaffected by any continuum resonance. Here, we report that the forward-backward asymmetry in the electron angular distribution, with respect to the photon axis, which is associated with photoelectron circular dichroism can surprisingly reverse direction according to the ion vibrational mode excited. This vibrational dependence represents a clear breakdown of the usual Franck–Condon assumption, ascribed to the enhanced sensitivity of photoelectron circular dichroism (compared with other observables like cross-sections or the conventional anisotropy parameter-β) to the scattering phase off the chiral molecular potential, inducing a dependence on the nuclear geometry sampled in the photoionization process. Important consequences for the interpretation of such dichroism measurements within analytical contexts are discussed.

Citation

Garcia, G. A., Nahon, L., Daly, S., & Powis, I. (2013). Vibrationally induced inversion of photoelectron forward-backward asymmetry in chiral molecule photoionization by circularly polarized light. Nature Communications, 4(2132), Article 2132. https://doi.org/10.1038/ncomms3132

Journal Article Type Article
Publication Date Jul 5, 2013
Deposit Date Mar 27, 2014
Publicly Available Date Mar 28, 2024
Journal Nature Communications
Electronic ISSN ESSN: 2041-1723
Publisher Nature Publishing Group
Peer Reviewed Peer Reviewed
Volume 4
Issue 2132
Article Number 2132
DOI https://doi.org/10.1038/ncomms3132
Public URL https://nottingham-repository.worktribe.com/output/716644
Publisher URL http://www.nature.com/ncomms/2013/130705/ncomms3132/full/ncomms3132.html#methods

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