Journal article
ClClO2 Is the Most Stable Isomer of Cl2O2. Accurate Coupled Cluster Energetics and Electronic Spectra of Cl2O2 Isomers
The journal of physical chemistry. A, Molecules, spectroscopy, kinetics, environment, & general theory, Vol.112(40), pp.9623-9627
10/09/2008
Handle:
https://hdl.handle.net/2376/104019
PMID: 18778040
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.
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Details
- Title
- ClClO2 Is the Most Stable Isomer of Cl2O2. Accurate Coupled Cluster Energetics and Electronic Spectra of Cl2O2 Isomers
- Creators
- Myrna H MatusMinh T NguyenDavid A DixonKirk A PetersonJoseph S Francisco
- Publication Details
- The journal of physical chemistry. A, Molecules, spectroscopy, kinetics, environment, & general theory, Vol.112(40), pp.9623-9627
- Academic Unit
- Chemistry, Department of
- Publisher
- American Chemical Society
- Identifiers
- 99900546651201842
- Language
- English
- Resource Type
- Journal article