title: ClClO2 is the most stable isomer of Cl2O2. 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 Cl2O2 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 ClClO2 absorb to longer wavelengths in the visible than do the singlet states of ClOOCl as does ClOClO.
authors.forename: Myrna H
authors.initials: MH
authors.lastname: Matus
authors.forename: Minh T
authors.initials: MT
authors.lastname: Nguyen
authors.forename: David A
authors.initials: DA
authors.lastname: Dixon
authors.forename: Kirk A
authors.initials: KA
authors.lastname: Peterson
authors.forename: Joseph S
authors.initials: JS
authors.lastname: Francisco