Giant Chiral Asymmetry in the C 1<i>s</i> Core Level Photoemission from Randomly Oriented Fenchone Enantiomers

Ulrich, Volker; Barth, Silko; Joshi, Sanjeev; Hergenhahn, U.; Mikajlo, Elisabeth; Harding, Christopher John; Powis, Ivan

doi:10.1021/jp709761u

Cited by 47 publications

(86 citation statements)

References 21 publications

(60 reference statements)

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“…Theoretical modelling of these results is aided by the rigid, bicyclic structure of camphor that consequently avoids the complications introduced by multiple conformations that are present in floppier molecules. The magnitude of the observed dichroism is in no way diminished in the carbonyl C=O 1s core ionizations, [5,11,12] despite the evidently achiral (spherical, localised) character of the initial 1s orbital. Evidently the chiral asymmetries detected in 1s core level photoemission stem from the final state scattering of the outgoing electron off the chiral molecular potential, an effect which for camphor could be closely reproduced by available computational treatments.…”

Section: Introductionmentioning

confidence: 89%

“…[12] These calculations have here been extended to provide predictions for several valence orbital ionizations. Full details of our use of the CMS-Xa method have been previously described.…”

Section: Computational Detailsmentioning

confidence: 99%

“…A recent paper has made this comparison for the core C 1s ionization; [12] here we present results pertaining…”

Section: Introductionmentioning

confidence: 97%

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A Valence Photoelectron Imaging Investigation of Chiral Asymmetry in the Photoionization of Fenchone and Camphor

et al. 2008

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Photoelectron circular dichroism (PECD) is investigated in the valence ionization of selected fenchone enantiomers using a photoelectron imaging technique and circularly polarized synchrotron radiation. Theoretical modelling of the results using electron scattering calculations demonstrates that the observed chiral asymmetry in the photoelectron angular distributions depends strongly upon the final state scattering, and upon the quality of the molecular potential used for these calculations. However, very pronounced dependence on the orbital from which ionization occurs is also observed. Comparison with analogous results previously obtained for camphor reveals striking differences in the PECD, even when the ionizing orbitals are themselves left substantially unaffected by the changes in methyl groups' substitution site. PECD measurements readily differentiate these molecules despite their very similar photoelectron spectra, demonstrating PECD to be a structurally sensitive probe.

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Section: Introductionmentioning

confidence: 89%

Section: Computational Detailsmentioning

confidence: 99%

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A Valence Photoelectron Imaging Investigation of Chiral Asymmetry in the Photoionization of Fenchone and Camphor

et al. 2008

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“…Finally, this sensitivity to isomerism confirms also that PECD is a long--range effect, at least for slow electrons, since in the case of camphor the methyl groups are localized quite far from the site of the ionized orbital. Because PECD happens during the scattering process, it also observed upon inner--shell ionization from spherical orbitals, and some difference have also been found in the PECD from C1s ionization of camphor and fenchone 55 . However these differences, mainly observed along the shape resonance above 10 eV KE, are much smaller than what is observed here for outer valence shell electrons.…”

Section: Camphor/fenchone Comparison : Sensitivity To Isomerismmentioning

confidence: 99%

Determination of accurate electron chiral asymmetries in fenchone and camphor in the VUV range: sensitivity to isomerism and enantiomeric purity

Nahon

Nag

Garcia

et al. 2016

Phys. Chem. Chem. Phys.

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121

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Ivan (2016) Determination of accurate electron chiral asymmetries in fenchone and camphor in the VUV range: sensitivity to isomerism and enantiomeric purity. Physical Chemistry Chemical Physics . ISSN 1463-9084 Access from the University of Nottingham repository: http://eprints.nottingham.ac.uk/32734/1/PECD_PCCP2016_Accepted_manuscript.pdf Copyright and reuse:The Nottingham ePrints service makes this work by researchers of the University of Nottingham available open access under the following conditions. This article is made available under the University of Nottingham End User licence and may be reused according to the conditions of the licence. For more details see: http://eprints.nottingham.ac.uk/end_user_agreement.pdf A note on versions:The version presented here may differ from the published version or from the version of record. If you wish to cite this item you are advised to consult the publisher's version. Please see the repository url above for details on accessing the published version and note that access may require a subscription.For more information, please contact eprints@nottingham.ac.uk This is an Accepted Manuscript, which has been through the Royal Society of Chemistry peer review process and has been accepted for publication.Accepted Manuscripts are published online shortly after acceptance, before technical editing, formatting and proof reading. Using this free service, authors can make their results available to the community, in citable form, before we publish the edited article. We will replace this Accepted Manuscript with the edited and formatted Advance Article as soon as it is available.You can find more information about Accepted Manuscripts in the Information for Authors.Please note that technical editing may introduce minor changes to the text and/or graphics, which may alter content. Photoelectron circular dichroism (PECD) manifests itself as an intense forward/backward asymmetry in the angular distribution of photoelectrons produced from randomly--oriented enantiomers by photoionization with circularly--polarized light (CPL). As a sensitive probe of both photoionization dynamics and of the chiral molecular potential, PECD attracts much interest especially with the recent performance of related experiments with visible and VUV laser sources. Here we report, by use of quasi--perfect CPL VUV synchrotron radiation and using a double imaging photoelectron/photoion coincidence (i 2 PEPICO) spectrometer, new and very accurate values of the corresponding asymmetries on showcase chiral isomers: camphor and fenchone. These data have additionally been normalized to the absolute enantiopurity of the sample as measured by a chromatographic technique. They can therefore be used as benchmarking data for new PECD experiments, as well as for theoretical models. In particular we found, especially for the outermost orbital of both molecules, a good agreement with CMS--Xα PECD modeling over the whole VUV range. We also report a spectacular sensitivity of PECD to isomerism for slow electrons, ...

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“…22 This hybrid set of atomic sphere radii has recently been established to work well in rather large molecules such as fenchone. 10 The CMS_Xa calculations work with a set of angular basis functions located on each atomic site, while the radial functions are obtained directly by numerical integration. The angular basis requires truncation at some appropriate values of the angular momentum, l max .…”

Section: Computational Detailsmentioning

confidence: 99%

Photoelectron circular dichroism: Chiral asymmetry in the angular distribution of electrons emitted by (+)‐S‐carvone

Powis

2008

Chirality

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The technique of photoelectron circular dichroism (PECD) is introduced and illustrated by the presentation of results obtained for the C 1s core ionization of (+)-S-carvone enantiomers. Using circularly polarized ionizing radiation, large chiral effects in the angular distribution of photoelectrons emitted from a dilute, randomly oriented gas phase sample can be detected. This effect is predicted in the pure electric dipole approximation and is expected to be quite general. The forward-backward asymmetry regularly exceeds 10%, as demonstrated here for the carbonyl C 1s photoemission of carvone. Calculations are presented that reveal a pronounced dependence of this effect on molecular conformation. In the case of carvone the PECD associated with the C 1s electron localized at the carbonyl group varies with orientation of the isopropenyl tail group at the opposite end of the molecule. Comparisons of calculations with experiment confirm the molecular configuration and permit inferences to be drawn concerning the relative conformer populations in the experimental sample.

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Giant Chiral Asymmetry in the C 1s Core Level Photoemission from Randomly Oriented Fenchone Enantiomers

Cited by 47 publications

References 21 publications

A Valence Photoelectron Imaging Investigation of Chiral Asymmetry in the Photoionization of Fenchone and Camphor

A Valence Photoelectron Imaging Investigation of Chiral Asymmetry in the Photoionization of Fenchone and Camphor

Determination of accurate electron chiral asymmetries in fenchone and camphor in the VUV range: sensitivity to isomerism and enantiomeric purity

Photoelectron circular dichroism: Chiral asymmetry in the angular distribution of electrons emitted by (+)‐S‐carvone

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