Dynamics and mode specificity in OClO photodissociation

Journal Article · Thu Jul 09 04:00:00 EDT 1992 · Journal of Physical Chemistry

DOI:https://doi.org/10.1021/j100193a005· OSTI ID:273691

Davis, H F; Yuan, T L ^[1]

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1. Lawrence Berkeley Laboratory, CA (United States)

The photodissociation of OClO in a molecular beam was studied using photofragment translational energy spectroscopy at wavelengths between 350 and 475 nm. Although the dominant products are ClO(x{sup 2}II) + O({sup 3}P), the authors observe formation of Cl({sup 2}P) + O{sub 2}({sup 3}{Sigma}{sub g}{sup {minus}}) and find strong evidence for a substantial yield of Cl({sup 2}P) + O{sub 2}({sup 1}{Delta}{sub g}). The total yield reaches a maximum of 3.9 {plus_minus} 0.8% near 404 nm and decreases to <0.2% under the absorption peaks in the wavelength range 350-370 nm. The branching ratios display mode specificity: the yield of Cl + O{sub 2} from OClO with symmetric stretching excitation or symmetric stretching + bending is {approximately} 10 times greater than from states at nearly the same energy with asymmetric stretching excitation. The Cl + O{sub 2} results from concerted unimolecular decomposition with release of up to {approximately} 68 kcal/mol in relative translational energy. 25 refs., 6 figs.

• Sponsoring Organization: USDOE
• OSTI ID: 273691
• Journal Information: Journal of Physical Chemistry, Journal Name: Journal of Physical Chemistry Journal Issue: 14 Vol. 96; ISSN JPCHAX; ISSN 0022-3654
• Country of Publication: United States
• Language: English

Related Subjects

40 CHEMISTRY
CHEMICAL REACTION YIELD
CHLORINE OXIDES
DISSOCIATION
MOLECULAR BEAMS
PHOTOCHEMICAL REACTIONS