Theoretical investigation of the O({sup 3}P) + CHX{sub 2} (X = F, Cl) reactions

Journal Article · Thu Oct 07 04:00:00 EDT 1999 · Journal of Physical Chemistry A: Molecules, Spectroscopy, Kinetics, Environment, amp General Theory

DOI:https://doi.org/10.1021/jp990907n· OSTI ID:20001103

Hou, H; Wang, B; Gu, Y

The reactions of oxygen atoms with the CHX{sub 2} (X = F, Cl) radicals have been studied for the first time using the G2(MP2) method. The extensive calculations reveal the capture-limited association-elimination mechanism for the O + CHX{sub 2} reaction. For the O({sup 3}P) + CHF{sub 2} reaction, two energy-rich intermediates, CHF{sub 2}O* and CF{sub 2}OH*, are formed along the reaction path. CHF{sub 2}O* has four unimolecular production channels: H + CF{sub 2}O; CF{sub 2}OH; F + CHFO; and HF + FCO. The isomer CF{sub 2}OH can decompose to H + CF{sub 2}O, HF + FCO, OH + CF{sub 2}, and F + FCOH. The analogous production channels such as Cl + CHClO, H + CCl{sub 2}O, HCl + ClCO, OH + CCl{sub 2}, and Cl + ClCOH are investigated for the O({sup 3}P) + CHCl{sub 2} reaction. It should be noted that three-center direct elimination of HCl from the adduct CHCl{sub 2}O* was characterized using the semiempirical AMl method. On the basis of the ab initio potential energy surfaces, the kinetics and the dynamics for these two atom/radical reactions are discussed qualitatively. For the O + CHF{sub 2} reaction, H and CF{sub 2}O are predicted to be the major products. For the O({sup 3}P) + CHCl{sub 2} reaction, the major production channel is the formation of Cl + CHClO, while the HCl + ClCO channel may be competitive.

• Research Organization: Shandong Univ., Jinan (CN)
• OSTI ID: 20001103
• Journal Information: Journal of Physical Chemistry A: Molecules, Spectroscopy, Kinetics, Environment, amp General Theory, Journal Name: Journal of Physical Chemistry A: Molecules, Spectroscopy, Kinetics, Environment, amp General Theory Journal Issue: 40 Vol. 103; ISSN 1089-5639; ISSN JPCAFH
• Country of Publication: United States
• Language: English

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