Papers on Atmospheric Chemistry
Ab initio study of XOClO3 (X = Cl, F, and H): Implications for formation of ClOClO3 in the stratosphere
Article first published online: 21 SEP 2012
Copyright 1997 by the American Geophysical Union.
Journal of Geophysical Research: Atmospheres (1984–2012)
Volume 102, Issue D11, pages 12927–12935, 20 June 1997
How to Cite
1997), Ab initio study of XOClO3 (X = Cl, F, and H): Implications for formation of ClOClO3 in the stratosphere, J. Geophys. Res., 102(D11), 12927–12935, doi:10.1029/97JD00008., , and (
- Issue published online: 21 SEP 2012
- Article first published online: 21 SEP 2012
- Manuscript Accepted: 31 DEC 1996
- Manuscript Received: 27 MAR 1996
Although OClO photolysis was one of the first photochemical reactions to be studied, the primary photochemistry of OClO still remains controversial. Several studies have demonstrated that Cl2O4 is one of the major photolysis products of OClO, in addition to ClO + O and ClOO. Thus there is a need to analyze the chemical properties of Cl2O4 and its related species. In the present study we have investigated the equilibrium structures and harmonic vibrational frequencies of chlorine perchlorate (Cl2O4), fluorine perchlorate (FOClO3), and hydrogen perchlorate (HOClO3) at Hartree-Fock and MP2 levels using 6–31G* basis set. Normal mode analysis has been carried out using ab initio derived force fields at the correlation level for the 6–31G* basis set. The calculated frequencies of XOClO3 (X = Cl, F, and H) molecules are discussed in comparison with those determined from experiment and with the corresponding vibrations of Cl2O7. In addition, the paper draws attention to the possible role of C12O4 formation in the polar stratosphere with relevance to ozone layer depletion.