Density functional study of chlorine-oxygen compounds related to the ClO self-reaction

• Published in: International journal of quantum chemistry Vol. 66; no. 3; pp. 203 - 217
• Main Authors: Fängström, Torbjörn, Edvardsson, David, Ericsson, Marie, Lunell, Sten, Enkvist, Christer
• Format: Journal Article
• Language: English
• Published: New York John Wiley & Sons, Inc 1998
• Subjects: 3 ISOMERS; Chemistry; CONFIGURATION-INTERACTION; CORRELATION-ENERGY; CRYOGENIC MATRICES; GAUSSIAN-BASIS SETS; INFRARED-SPECTRUM; Kemi; Kvantkemi; MOLECULAR CALCULATIONS; MOLLER-PLESSET; NATURAL SCIENCES; NATURVETENSKAP; OXIDE DIMER; Quantum chemistry; Teoretisk kemi; Theoretical chemistry; VIBRATIONAL FREQUENCIES
• ISSN: 0020-7608; 1097-461X; 1097-461X
• DOI: 10.1002/(SICI)1097-461X(1998)66:3<203::AID-QUA2>3.0.CO;2-Z

Geometrical parameters, vibrational frequencies, relative stabilities, and dissociation energies of the three stable Cl2O2 isomers and the OClO and ClOO radicals were investigated by density functional theory (DFT). The present analysis shows that DFT using hybrid functionals is capable of describing these systems to at least the same degree of accuracy as ab initio methods. The average absolute bond‐length deviation of ClClO2, ClOOCl, and ClO2 from experimental results is 0.024/0.027 Å, with a maximum deviation for the dichlorine peroxide O(SINGLE BOND)O bond equal to 0.072/0.063 Å, for the B3PW91 and B3LYP functionals, respectively. The average absolute bond‐angle deviation for the hybrid functionals is 0.8°. Harmonic vibrational frequencies calculated with DFT give for all Cl(SINGLE BOND)O compounds good agreement with experiments. The dissociation energies of ClOOCl, OClO, and ClOO were found to be in good agreement with experiments, the average error being less than 1.2 kcal/mol. The two isomers chloryl chloride (ClClO2) and dichlorine peroxide (ClOOCl) were found to be approximately 9 kcal/mol more stable than the chlorine chlorite (ClOClO) isomer. The ClOO isomer is predicted to be 3.0 kcal/mol more stable than OClO, in accordance with the experimental value of 4 kcal/mol. © 1998 John Wiley & Sons, Inc. Int J Quant Chem 66: 203–217, 1998