In:
ChemPhysChem, Wiley, Vol. 6, No. 6 ( 2005-06-13), p. 1164-1168
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 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 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.
Type of Medium:
Online Resource
ISSN:
1439-4235
,
1439-7641
DOI:
10.1002/cphc.200400483
Language:
English
Publisher:
Wiley
Publication Date:
2005
detail.hit.zdb_id:
2025223-7
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