On the chemical bond of ClO2: An ab initio study

Abstract

The simple ClO₂ (C_2v) radical exhibits an interesting chemical bonding and is studied using an adiabatic–to–diabatic transformation at the MRCI/aug-cc-pV(Q + d)Z computational level. We propose the existence of two types of bonds between Cl and the terminal O atoms. A simple 2 center/2 e⁻ ClO bond originating from Cl (²P, $M_L=0$) + O (³P, $M_L=\pm 1$) and another one that diabatically results from the interaction of ClO ($X{}^2\Pi$) + O (¹D) and thus classified as a dative one. The radical center is primarily delocalized over the terminal O atoms but can also be found on Cl due to the involvement of an excited ClO state.