title: Angle-resolved photoelectron spectroscopy of randomly oriented 3-hydroxytetrahydrofuran enantiomers.
abstract: Circular dichroism in the angular distribution of valence photoelectrons emitted from randomly oriented 3-hydroxytetrahydrofuran enantiomers (ThS and ThR) has been observed in gas-phase experiments using circularly polarized vacuum ultraviolet (VUV) light. The measured dichroism for both ThS and ThR, acquired at the single magic angle theta=234.73 degrees and at photon energies of 22, 19, 16, and 14 eV, points to an asymmetric forward-backward scattering of the photoelectrons from their highest occupied molecular orbitals (HOMO) HOMO-1 and HOMO-2, of up to 5%, depending on the photon energy. The asymmetry reverses on exchange of either the helicity of the radiation or the configuration of Th. The photoionization dichroic D parameters of ThS and ThR have been measured and their values discussed in the light of LCAO B-spline density functional theory (DFT) predictions. While an acceptable agreement is found between the dichroic parameter measured and calculated at the highest photon energy for the HOMO and HOMO-2 orbitals of Th, a significant discrepancy is observed for the HOMO-1 state which is attributed to the floppiness of Th, in particular to the comparatively large sensitivity of the size and shape of its HOMO-1 on nuclear vibrational motion.
authors.affiliation: Dipartimento di Chimica, Università di Roma La Sapienza, Pl. A. Moro 5, 00185 Roma, Italy.
authors.forename: Anna
authors.initials: A
authors.lastname: Giardini
authors.forename: Daniele
authors.initials: D
authors.lastname: Catone
authors.forename: Stefano
authors.initials: S
authors.lastname: Stranges
authors.forename: Mauro
authors.initials: M
authors.lastname: Satta
authors.forename: Mario
authors.initials: M
authors.lastname: Tacconi
authors.forename: Susanna
authors.initials: S
authors.lastname: Piccirillo
authors.forename: Stefano
authors.initials: S
authors.lastname: Turchini
authors.forename: Nicola
authors.initials: N
authors.lastname: Zema
authors.forename: Giorgio
authors.initials: G
authors.lastname: Contini
authors.forename: Tommaso
authors.initials: T
authors.lastname: Prosperi
authors.forename: Pietro
authors.initials: P
authors.lastname: Decleva
authors.forename: Devis
authors.initials: D
authors.lastname: Di Tommaso
authors.forename: Giovanna
authors.initials: G
authors.lastname: Fronzoni
authors.forename: Mauro
authors.initials: M
authors.lastname: Stener
authors.forename: Antonello
authors.initials: A
authors.lastname: Filippi
authors.forename: Maurizio
authors.initials: M
authors.lastname: Speranza
mesh_terms: D002942:Circular Dichroism; D004583:Electrons; D005663:Furans / Q000737:chemistry*; D013237:Stereoisomerism
chemical_list: D005663:Furans