Electronic states of PCl2 and PCl2+

Spectroscopic constants and potential energy curves of several electronic states of PCl2 (X̃ 2B1, 2A1(I), 2A1(II), 2A2, 2Pg, 4Pg, 2B2 4Σg−, 4B1, 2B1(II)), 2B1(III)) and PCl2+ (1A1, 3B1 and 1B1) have been investigated using the complete active space self-consistent field (CASSCF) followed by multi-reference singles and doubles configuration interaction (MRSDCI) methods that included up to 1.2 million configurations. The bond dissociation energies of PCl and PCl2 as well as the adiabatic ionization energy of PCl2 are computed. The observed A−X system is reassigned to the Ã2B2−X̃ 2B1 transition.