The importance of molecular axis alignment and symmetry-breaking in photoelectron elliptical dichroism

Photoelectron angular distributions (PADs) produced from the photoionization of chiral molecules using elliptically polarized light exhibit a forward/backward asymmetry with respect to the optical propagation direction. By recording these distributions using the velocity-map imaging (VMI) technique,...

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Veröffentlicht in:The Journal of chemical physics 2023-12, Vol.159 (21)
Hauptverfasser: Sparling, Chris, Ruget, Alice, Ireland, Lewis, Kotsina, Nikoleta, Ghafur, Omair, Leach, Jonathan, Townsend, Dave
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container_issue 21
container_start_page
container_title The Journal of chemical physics
container_volume 159
creator Sparling, Chris
Ruget, Alice
Ireland, Lewis
Kotsina, Nikoleta
Ghafur, Omair
Leach, Jonathan
Townsend, Dave
description Photoelectron angular distributions (PADs) produced from the photoionization of chiral molecules using elliptically polarized light exhibit a forward/backward asymmetry with respect to the optical propagation direction. By recording these distributions using the velocity-map imaging (VMI) technique, the resulting photoelectron elliptical dichroism (PEELD) has previously been demonstrated as a promising spectroscopic tool for studying chiral molecules in the gas phase. The use of elliptically polarized laser pulses, however, produces PADs (and consequently, PEELD distributions) that do not exhibit cylindrical symmetry about the propagation axis. This leads to significant limitations and challenges when employing conventional VMI acquisition and data processing strategies. Using novel photoelectron image analysis methods based around Hankel transform reconstruction tomography and machine learning, however, we have quantified—for the first time—significant symmetry-breaking contributions to PEELD signals that are of a comparable magnitude to the symmetric terms in the multiphoton ionization of (1R,4R)-(+)- and (1S,4S)-(−)-camphor. This contradicts any assumptions that symmetry-breaking can be ignored when reconstructing VMI data. Furthermore, these same symmetry-breaking terms are expected to appear in any experiment where circular and linear laser fields are used together. This ionization scheme is particularly relevant for investigating dynamics in chiral molecules, but it is not limited to them. Developing a full understanding of these terms and the role they play in the photoionization of chiral molecules is of clear importance if the potential of PEELD and related effects for future practical applications is to be fully realized.
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subjects Asymmetry
Broken symmetry
Camphor
Data processing
Dichroism
Image acquisition
Image analysis
Image reconstruction
Ionization
Machine learning
Photoelectrons
Photoionization
Physics
Polarized light
Symmetry
Vapor phases
title The importance of molecular axis alignment and symmetry-breaking in photoelectron elliptical dichroism
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