title: Chiral signatures in angle-resolved valence photoelectron spectroscopy of pure glycidol enantiomers.
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-Xalpha) 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.
authors.affiliation: Synchrotron SOLEIL, l'Orme des Merisiers, Saint Aubin BP 48, 91192, Gif sur Yvette Cedex, France.
authors.forename: Gustavo A
authors.initials: GA
authors.lastname: Garcia
authors.forename: Laurent
authors.initials: L
authors.lastname: Nahon
authors.forename: Chris J
authors.initials: CJ
authors.lastname: Harding
authors.forename: Ivan
authors.initials: I
authors.lastname: Powis
mesh_terms: D000465:Algorithms; D002942:Circular Dichroism / Q000379:methods; D004852:Epoxy Compounds / Q000737:chemistry*; D008958:Models, Molecular; D008968:Molecular Conformation; D020005:Propanols / Q000737:chemistry*; D013057:Spectrum Analysis / Q000379:methods*; D013237:Stereoisomerism
chemical_list: D004852:Epoxy Compounds; D020005:Propanols; C004312:glycidol