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Angle‐Resolved Photoelectron Spectroscopy of Randomly Oriented 3‐Hydroxytetrahydrofuran Enantiomers
Author(s) -
Giardini Anna,
Catone Daniele,
Stranges Stefano,
Satta Mauro,
Tacconi Mario,
Piccirillo Susanna,
Turchini Stefano,
Zema Nicola,
Contini Giorgio,
Prosperi Tommaso,
Decleva Pietro,
Di Tommaso Devis,
Fronzoni Giovanna,
Stener Mauro,
Filippi Antonello,
Speranza Maurizio
Publication year - 2005
Publication title -
chemphyschem
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.016
H-Index - 140
eISSN - 1439-7641
pISSN - 1439-4235
DOI - 10.1002/cphc.200400483
Subject(s) - dichroic glass , photoionization , atomic physics , photon energy , chemistry , vibrational circular dichroism , density functional theory , dichroism , valence (chemistry) , atomic orbital , circular dichroism , spectroscopy , molecular physics , photon , physics , ionization , crystallography , electron , optics , computational chemistry , ion , organic chemistry , quantum mechanics
Circular dichroism in the angular distribution of valence photoelectrons emitted from randomly oriented 3‐hydroxytetrahydrofuran enantiomers ( ThSand ThR ) has been observed in gas‐phase experiments using circularly polarized vacuum ultraviolet (VUV) light. The measured dichroism for both ThSand ThR , acquired at the single magic angle θ=234.73 ° 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 ThSand ThRhave 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.