We report a joint experimental and theoretical study of circular dichroism in the valence photoelectron spectra of a free chiral molecule. The circular dichroism in photoelectron spectroscopy is measured at the magic angle for various valence states of R(+) and S(-) methyl-oxirane enantiomers in the vapor phase. The maximum dichroism measured is about 5x10(-2). Experimental and theoretical results are in agreement. The ab initio calculation employs a multicentric basis set of B-spline functions and a Kohn-Sham Hamiltonian.
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