Circular dichroism in photoelectron spectroscopy of free chiral molecules: Experiment and theory on methyl-oxirane

Abstract

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 $S(\ensuremath{-})$ methyl-oxirane enantiomers in the vapor phase. The maximum dichroism measured is about $5\ifmmode\times\else\texttimes\fi{}{10}^{\ensuremath{-}2}$. 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.