Structures, relative stabilities, and vibrational spectra of isomers of Cl sub 2 O sub 2 : The role of the chlorine oxide dimer in Antarctic ozone depleting mechanisms

Journal Article · Thu Jul 26 00:00:00 EDT 1990 · Journal of Physical Chemistry; (USA)

DOI:https://doi.org/10.1021/j100378a089· OSTI ID:6163031

McGrath, M P; Clemitshaw, K C; Rowland, F S; Hehre, W J ^[1]

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1. Univ. of California, Irvine (USA)

Quantitative ab initio molecular orbital calculations have been applied to he description of the structures, relative stabilities, and vibrational spectra of isomers of Cl{sub 2}O{sub 2}. The highest level of calculations performed (MP2/6-31+G (3d)//MP2/6-31G*) suggests that C{sub 2} symmetry ClOOCl (chlorine peroxide) is the lowest energy form but that the hypervalent, C{sub s} symmetry species ClClO{sub 2} (chloryl chloride) is only about 1 kcal/mol higher in energy. A third form, C{sub 1} symmetry ClOClO (chlorine chlorite), lies higher in energy by 7 kcal/mol. The theoretical results are compared with experimentally determined thermochemical and vibrational data, and the role of the chlorine oxide dimer in Antarctic ozone depleting mechanisms is discussed.

• OSTI ID: 6163031
• Journal Information: Journal of Physical Chemistry; (USA), Vol. 94:15; ISSN 0022-3654
• Country of Publication: United States
• Language: English

Related Subjects

54 ENVIRONMENTAL SCIENCES
ATMOSPHERIC CHEMISTRY
CHLORINE OXIDES
MOLECULAR STRUCTURE
STABILITY
VIBRATIONAL STATES
ANTARCTIC REGIONS
CALCULATION METHODS
MOLECULAR ORBITAL METHOD
OZONE LAYER
CHALCOGENIDES
CHEMISTRY
CHLORINE COMPOUNDS
ENERGY LEVELS
EXCITED STATES
HALOGEN COMPOUNDS
LAYERS
OXIDES
OXYGEN COMPOUNDS
POLAR REGIONS
540120* - Environment
Atmospheric- Chemicals Monitoring & Transport- (1990-)