Premium
A Valence Photoelectron Imaging Investigation of Chiral Asymmetry in the Photoionization of Fenchone and Camphor
Author(s) -
Powis Ivan,
Harding Chris J.,
Garcia Gustavo A.,
Nahon Laurent
Publication year - 2008
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.200700748
Subject(s) - photoionization , chemistry , valence (chemistry) , ionization , circular dichroism , valence electron , synchrotron radiation , molecular orbital , molecular physics , molecule , electron , crystallography , physics , organic chemistry , ion , optics , quantum mechanics
Photoelectron circular dichroism (PECD) is investigated in the valence ionization of selected fenchone enantiomers using a photoelectron imaging technique and circularly polarized synchrotron radiation. Theoretical modelling of the results using electron scattering calculations demonstrates that the observed chiral asymmetry in the photoelectron angular distributions depends strongly upon the final state scattering, and upon the quality of the molecular potential used for these calculations. However, very pronounced dependence on the orbital from which ionization occurs is also observed. Comparison with analogous results previously obtained for camphor reveals striking differences in the PECD, even when the ionizing orbitals are themselves left substantially unaffected by the changes in methyl groups’ substitution site. PECD measurements readily differentiate these molecules despite their very similar photoelectron spectra, demonstrating PECD to be a structurally sensitive probe.