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 Rs+d and Ss−d methyl-oxirane enantiomers in the vapor phase. The maximum dichroism measured is about 5310−2. 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.
