Vibrationally-resolved photoelectron spectroscopy and photoelectron circular dichroism of bicyclic monoterpene enantiomers

The photoionization of four chiral bicyclic monoterpene isomers, α-pinene, β-pinene, 3-carene and sabinene — all commonly found constituents in essential natural oils — has been studied using synchrotron radiation and compared to recent findings for the cyclic isomer limonene. Slow photoelectron spe...

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Main Authors: Ganjitabar, Hassan, Hadidi, Rim, Garcia, Gustavo A., Nahon, Laurent, Powis, Ivan
Format: Article
Language:English
Published: Elsevier 2018
Online Access:https://eprints.nottingham.ac.uk/55094/
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author Ganjitabar, Hassan
Hadidi, Rim
Garcia, Gustavo A.
Nahon, Laurent
Powis, Ivan
author_facet Ganjitabar, Hassan
Hadidi, Rim
Garcia, Gustavo A.
Nahon, Laurent
Powis, Ivan
author_sort Ganjitabar, Hassan
building Nottingham Research Data Repository
collection Online Access
description The photoionization of four chiral bicyclic monoterpene isomers, α-pinene, β-pinene, 3-carene and sabinene — all commonly found constituents in essential natural oils — has been studied using synchrotron radiation and compared to recent findings for the cyclic isomer limonene. Slow photoelectron spectra (SPES) are recorded between threshold and an energy of 10.5 eV. In the case of limonene, α-pinene, and 3-carene, vibrational structure is observed in the ground ionic state and attributed to a CC double bond stretching in the cation, using Franck-Condon vibrational band simulations. The photoelectron circular dichroism (PECD) is examined for specific enantiomers of these terpenes, and vibrational modification of the forward-backward photoelectron asymmetry detected by PECD can be tentatively identified, even when the corresponding SPES is unstructured. Large chiral asymmetry factors are found at low binding energies for the pinenes and 3-carene, with α-pinene in particular displaying a 37% forward-backward photoelectron asymmetry, believed to be a record chiroptical asymmetry for randomly-oriented, non-interacting molecules.
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spelling nottingham-550942020-08-23T04:30:10Z https://eprints.nottingham.ac.uk/55094/ Vibrationally-resolved photoelectron spectroscopy and photoelectron circular dichroism of bicyclic monoterpene enantiomers Ganjitabar, Hassan Hadidi, Rim Garcia, Gustavo A. Nahon, Laurent Powis, Ivan The photoionization of four chiral bicyclic monoterpene isomers, α-pinene, β-pinene, 3-carene and sabinene — all commonly found constituents in essential natural oils — has been studied using synchrotron radiation and compared to recent findings for the cyclic isomer limonene. Slow photoelectron spectra (SPES) are recorded between threshold and an energy of 10.5 eV. In the case of limonene, α-pinene, and 3-carene, vibrational structure is observed in the ground ionic state and attributed to a CC double bond stretching in the cation, using Franck-Condon vibrational band simulations. The photoelectron circular dichroism (PECD) is examined for specific enantiomers of these terpenes, and vibrational modification of the forward-backward photoelectron asymmetry detected by PECD can be tentatively identified, even when the corresponding SPES is unstructured. Large chiral asymmetry factors are found at low binding energies for the pinenes and 3-carene, with α-pinene in particular displaying a 37% forward-backward photoelectron asymmetry, believed to be a record chiroptical asymmetry for randomly-oriented, non-interacting molecules. Elsevier 2018-11-30 Article PeerReviewed application/pdf en cc_by_nc_nd https://eprints.nottingham.ac.uk/55094/1/Circular%201-s2.0-S0022285218301759-main.pdf Ganjitabar, Hassan, Hadidi, Rim, Garcia, Gustavo A., Nahon, Laurent and Powis, Ivan (2018) Vibrationally-resolved photoelectron spectroscopy and photoelectron circular dichroism of bicyclic monoterpene enantiomers. Journal of Molecular Spectroscopy, 353 . pp. 11-19. ISSN 0022-2852 http://dx.doi.org/10.1016/j.jms.2018.08.007 doi:10.1016/j.jms.2018.08.007 doi:10.1016/j.jms.2018.08.007
spellingShingle Ganjitabar, Hassan
Hadidi, Rim
Garcia, Gustavo A.
Nahon, Laurent
Powis, Ivan
Vibrationally-resolved photoelectron spectroscopy and photoelectron circular dichroism of bicyclic monoterpene enantiomers
title Vibrationally-resolved photoelectron spectroscopy and photoelectron circular dichroism of bicyclic monoterpene enantiomers
title_full Vibrationally-resolved photoelectron spectroscopy and photoelectron circular dichroism of bicyclic monoterpene enantiomers
title_fullStr Vibrationally-resolved photoelectron spectroscopy and photoelectron circular dichroism of bicyclic monoterpene enantiomers
title_full_unstemmed Vibrationally-resolved photoelectron spectroscopy and photoelectron circular dichroism of bicyclic monoterpene enantiomers
title_short Vibrationally-resolved photoelectron spectroscopy and photoelectron circular dichroism of bicyclic monoterpene enantiomers
title_sort vibrationally-resolved photoelectron spectroscopy and photoelectron circular dichroism of bicyclic monoterpene enantiomers
url https://eprints.nottingham.ac.uk/55094/
https://eprints.nottingham.ac.uk/55094/
https://eprints.nottingham.ac.uk/55094/