Perturbation analysis and constants for the red system of the cyanide radical

Abstract

A χ 2 test has been used to obtain improved molecular constants for the A 2Φ- X 2Σ system of the C 12N 14 radical. The new constants predict wavenumbers that agree with the observed valued to 0.1 Å for rotational levels up to N” = 80 for the lower vibrational bands and up to N“ = 50 for the higher bands. Wavenumbers for the (2,0) and (3,1) vibration-bands of the C 13N 14 radical have also been computed with these molecular constants. They agree to 0.1 Å with the measurements of Wyller (11) if the electronic isotope shift between the electronic states of the C 12N 14 radical is 0.2 cm -1. In the present calculations, the effect of degenerate perturbations between the 2Φ and 2Σ states is included.