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Issue 12, 2008
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Chiral signatures in angle-resolved valence photoelectron spectroscopy of pure glycidol enantiomers

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Abstract

Photoionization of the chiral molecule glycidol has been investigated in the valence region. Photoelectron circular dichroism (PECD) curves have been obtained at various photon energies by using circularly polarized VUV synchrotron radiation and a velocity map imaging technique to record angle-resolved photoelectron spectra (PES). The measured chiral asymmetries vary dramatically with the photon energy as well as with the ionized orbital, improving the effective orbital resolution of the PECD spectrum with respect to the PES. Typical asymmetry factors of 5% are observed, but the peak values measured range up to 15%. The experimental results are interpreted by continuum multiple scattering (CMS-Xα) calculations for several thermally accessible glycidol conformers. We find that a nearly quantitative agreement between theory and experiments can be achieved for the ionization of several molecular orbitals. Owing to the sensitivity of PECD to molecular conformation this allows us to identify the dominant conformer. The influence of intramolecular hydrogen bond orbital polarization is found to play a small yet significant role in determining the chiral asymmetry in the electron angular distributions.

Graphical abstract: Chiral signatures in angle-resolved valence photoelectron spectroscopy of pure glycidol enantiomers

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Publication details

The article was received on 12 Sep 2007, accepted on 19 Dec 2007 and first published on 31 Jan 2008


Article type: Paper
DOI: 10.1039/B714095A
Citation: Phys. Chem. Chem. Phys., 2008,10, 1628-1639
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    Chiral signatures in angle-resolved valence photoelectron spectroscopy of pure glycidol enantiomers

    G. A. Garcia, L. Nahon, C. J. Harding and I. Powis, Phys. Chem. Chem. Phys., 2008, 10, 1628
    DOI: 10.1039/B714095A

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