Circular dichroism in the angular distribution of valence photoelectrons emitted from randomly oriented 3-hydroxytetrahydrofuran enantiomers (Th-S and Th-R) has been observed in gas-phase experiments using circularly polarized vacuum ultraviolet (VUV) light. The measured dichroism for both Th-S and Th-R, 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 Th-S and Th-R 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.

Giardini, A., Catone, D., Stranges, S., Satta, M., Tacconi, M., Piccirillo, S., et al. (2005). Angle-resolved photoelectron spectroscopy of randomly oriented 3-hydroxytetrahydrofuran enantiomers, 6(6), 1164-1168 [10.1002/cphc.200400483].

Angle-resolved photoelectron spectroscopy of randomly oriented 3-hydroxytetrahydrofuran enantiomers

PICCIRILLO, SUSANNA;
2005-01-01

Abstract

Circular dichroism in the angular distribution of valence photoelectrons emitted from randomly oriented 3-hydroxytetrahydrofuran enantiomers (Th-S and Th-R) has been observed in gas-phase experiments using circularly polarized vacuum ultraviolet (VUV) light. The measured dichroism for both Th-S and Th-R, 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 Th-S and Th-R 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.
2005
Pubblicato
Rilevanza internazionale
Articolo
Sì, ma tipo non specificato
Settore CHIM/03 - CHIMICA GENERALE E INORGANICA
English
Con Impact Factor ISI
Chirality; Circular dichroism; Crossed-beam experiments; Photoelectron spectroscopy; Synchrotron radiation
furan derivative; article; chemistry; circular dichroism; electron; stereoisomerism; Circular Dichroism; Electrons; Furans; Stereoisomerism
Giardini, A., Catone, D., Stranges, S., Satta, M., Tacconi, M., Piccirillo, S., et al. (2005). Angle-resolved photoelectron spectroscopy of randomly oriented 3-hydroxytetrahydrofuran enantiomers, 6(6), 1164-1168 [10.1002/cphc.200400483].
Giardini, A; Catone, D; Stranges, S; Satta, M; Tacconi, M; Piccirillo, S; Turchini, S; Zema, N; Contini, G; Prosperi, T; Decleva, P; Di Tommaso, D; Fronzoni, G; Stener, M; Filippi, A; Speranza, M
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Utilizza questo identificativo per citare o creare un link a questo documento: https://hdl.handle.net/2108/57620
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