ClClCO2 is the most stable isomer of Cl2O 2. Accurate coupled cluster energetics and electronic spectra of Cl2O2 isomers

Abstract

High level ab initio electronic structure calculations at the coupled cluster level with a correction for triples (CCSD(T)) extrapolated to the complete basis set limit have been made for the thermodynamics of the Cl 2O2 isomers: ClClO2, ClOOCl, and ClOClO. The ClClO2 isomer is predicted to be the most stable isomer and is more stable than ClOOCl by 3.1 kcal/mol at 298 K. The ClOClO isomer is less stable than ClOOCl by 8.3 kcal/mol at 298 K. The weakest bond in ClClO2 is the Cl-Cl bond with a bond dissociation energy (BDE) of 24.4 kcal/mol, and the smallest BDE in ClOOCl is the O-O bond with a value of 18.0 kcal/mol. The smallest BDE in ClOClO is for the central O-Cl bond with a BDE of 9.7 kcal/mol. Electronic transitions were calculated with the equations of motion EOM-CCSD method. The calculations clearly demonstrate that singlet states of ClClO 2 absorb to longer wavelengths in the visible than do the singlet states of ClOOCl as does ClOClO. © 2008 American Chemical Society.