Complete description of linear molecule photoionization achieved by vector correlations using the light of a single circular polarization

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 (4sigma)(-1) inner-valence ionization is induced by left-handed circularly polarized synchrotron radiation at hnu=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. (C) 2003 American Institute of Physics.