Dynamical Auger emission induced by multistate vibronic coupling in the core-excited states of the BCl3 molecule

The Anger emission following the resonant excitation of the BCl3 molecule has been investigated using monochromatized synchrotron radiation. The B Is excitation to the unoccupied Anti-bonding 4e' orbital enhances the shoulder structure in the low kinetic energy side of the photoemission from the 2e' valence bonding orbital. Based on a series of quantum mechanical calculations, this shoulder structure is interpreted as the dynamical Auger emission which reflects the B-Cl stretching nuclear motion and appears as a result of the purely multistate vibronic coupling effect among the Jahn-Teller split B 1s(-1)4e' E' states and the closely lying B 1s(-1)3a'(1) A'(1) state.