Ab initio investigation of the 3Π states of NO⁺

Abstract

MCSCF + CI calculations on the five lowest 3Π states of NO+ strongly indicate transitions to the b 3Π state have been observed in the laser photofragment spectroscopy experiment by Cosby and Helm [J. Chem. Phys. 75, 3882 (1981)]. The 2 3Π state is shown to have a long range minimum bound with respect to separated atoms and a local minimum near R = 1.2 Å which gives rise to a quasibound state 0.81 eV above the N +(3P) + O(3P) asymptote or 21.84 eV above ground state NO. This quasibound state is responsible for the prominent feature at 21.7 eV in the photoelectron spectrum of NO, which was previously assigned to a c3Π state. © 1984 American Institute of Physics.