In this paper we demonstrate that the vector correlation approach for the study of dissociative photoionization (DPI) of linear molecules enables us to achieve a complete description of molecular photoionization by performing a single experiment using only one state of circularly, or elliptically, polarized light. This is illustrated by the derivation of the complex dipole matrix elements for the benchmark DPI reaction of the NO molecule, where (4σ)−1 inner-valence ionization is induced by left-handed circularly polarized synchrotron radiation at hν=23.65 eV. The importance of electronic correlation for this process is emphasized by comparing the experimental results with multichannel Schwinger configuration interaction calculations. The energy dependence of the transition matrix elements and that of the electronic correlation in the 25–40 eV energy range are illustrated by the calculations and compared with the present results and recent experimental studies at 40.8 eV.
Circular dichroism in the angular distribution of valence photoelectrons emitted from randomly oriented chiral molecules has been observed in experiments that use circularly polarized VUV synchrotron radiation. Photoionization of the outermost carbonyl oxygen lone pair electrons from pure enantiomers of the prototype chiral molecule camphor is shown to have an asymmetry in the forward–backward scattering of photoelectrons (relative to the propagation direction of the light beam) of magnitude approaching 3% at 9.2 eV photon energy. The asymmetry reverses on exchange of either the helicity of the radiation or of the molecular enantiomer, confirming theoretical predictions of an effect that arises in the pure electric-dipole approximation.
scite is a Brooklyn-based organization that helps researchers better discover and understand research articles through Smart Citations–citations that display the context of the citation and describe whether the article provides supporting or contrasting evidence. scite is used by students and researchers from around the world and is funded in part by the National Science Foundation and the National Institute on Drug Abuse of the National Institutes of Health.