Open AccessAb initio study of XOClO 3 (X = Cl, F, and H): Implications for formation of ClOClO 3 in the stratosphere
Author(s) -
Parthiban S.,
Raghunandan B. N.,
Sumathi R.
Publication year - 1997
Publication title -
journal of geophysical research: atmospheres
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.67
H-Index - 298
eISSN - 2156-2202
pISSN - 0148-0227
DOI - 10.1029/97jd00008
Subject(s) - perchlorate , stratosphere , ab initio , photodissociation , basis set , ab initio quantum chemistry methods , chemistry , ozone , atomic physics , molecule , computational chemistry , physics , ion , photochemistry , density functional theory , meteorology , organic chemistry
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 Cl 2 O 4 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 Cl 2 O 4 and its related species. In the present study we have investigated the equilibrium structures and harmonic vibrational frequencies of chlorine perchlorate (Cl 2 O 4 ), fluorine perchlorate (FOClO 3 ), and hydrogen perchlorate (HOClO 3 ) 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 XOClO 3 (X = Cl, F, and H) molecules are discussed in comparison with those determined from experiment and with the corresponding vibrations of Cl 2 O 7 . In addition, the paper draws attention to the possible role of C1 2 O 4 formation in the polar stratosphere with relevance to ozone layer depletion.