The A2Πi–X2Πi band system of ClO: Reinvestigation of the absorption spectrum

Abstract

The A2Πi–X2Πi band system of 35ClO has been reinvestigated in absorption in the flash photolysis of ClO2 and Cl2/O2 mixtures, using higher resolving power than in earlier work. The rotational assignments for the ν′–0 progression have been revised and extended and new molecular constants have been obtained. In addition, four new bands with ν″ = 1 and 2 have been observed for the first time. The value for the ground state vibrational interval is found to be [Formula: see text]. Widths are given for levels with 2 ≤ ν′ ≤ 25 and show that all these levels are predissociated. With the help of the theory of long-range interactions, an improved value for the ground state dissociation energy is obtained, viz. D0″ = 22 184 ± 3 cm−1 (≡ 63.427 ± 0.008 kcal/mole ≡ 2.7504 ± 0.0004 eV).