Crossed-beams and theoretical studies of the O( 3P) + H 2O → HO 2 + H reaction excitation function

Amy L. Brunsvold, Jianming Zhang, Hari P. Upadhyaya, Timothy K. Minton, Jon P. Camden, Jeffrey T. Paci, George C Schatz

Research output: Contribution to journalArticle

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Abstract

Hyperthermal collisions of ground-state atomic oxygen with H 2O have been investigated, with special attention paid to the H-atom elimination reaction, O( 3P) + H 2O(X 1A 1) → HO 2( 2A′) + H( 2S). This reaction was observed in a crossed-beams experiment, and the relative excitation function in the region around its energy threshold (50-80 kcal mol -1) was measured. Direct dynamics calculations were also performed at two levels of theory, B3LYP/6-31G(d,p) and MP2/6-31G(d,p). The shape of the B3LYP excitation function closely matches that of the experiment. The calculations provided a detailed description of the dynamics and revealed a striking dependence of the reaction mechanism on collision energy, where the cross section rises from a threshold near 60 kcal mol -1 to a peak at ∼115 kcal mol -1 and then decreases at higher energies as secondary dissociation of the internally excited HO 2 product becomes dominant. The calculations show that the cross section for H-atom elimination (O + H 2O → HO 2 + H) is about 10-25% that of the H-atom abstraction (O + H 2O → OH + OH) cross section for collision energies in the 70-160 kcal mol -1 range.

Original languageEnglish
Pages (from-to)10907-10913
Number of pages7
JournalJournal of Physical Chemistry A
Volume111
Issue number43
DOIs
Publication statusPublished - Nov 1 2007

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Atoms
excitation
collisions
elimination
cross sections
atoms
Ground state
thresholds
energy
Experiments
Oxygen
dissociation
ground state
oxygen
products

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry

Cite this

Brunsvold, A. L., Zhang, J., Upadhyaya, H. P., Minton, T. K., Camden, J. P., Paci, J. T., & Schatz, G. C. (2007). Crossed-beams and theoretical studies of the O( 3P) + H 2O → HO 2 + H reaction excitation function. Journal of Physical Chemistry A, 111(43), 10907-10913. https://doi.org/10.1021/jp0744228

Crossed-beams and theoretical studies of the O( 3P) + H 2O → HO 2 + H reaction excitation function. / Brunsvold, Amy L.; Zhang, Jianming; Upadhyaya, Hari P.; Minton, Timothy K.; Camden, Jon P.; Paci, Jeffrey T.; Schatz, George C.

In: Journal of Physical Chemistry A, Vol. 111, No. 43, 01.11.2007, p. 10907-10913.

Research output: Contribution to journalArticle

Brunsvold, AL, Zhang, J, Upadhyaya, HP, Minton, TK, Camden, JP, Paci, JT & Schatz, GC 2007, 'Crossed-beams and theoretical studies of the O( 3P) + H 2O → HO 2 + H reaction excitation function', Journal of Physical Chemistry A, vol. 111, no. 43, pp. 10907-10913. https://doi.org/10.1021/jp0744228
Brunsvold AL, Zhang J, Upadhyaya HP, Minton TK, Camden JP, Paci JT et al. Crossed-beams and theoretical studies of the O( 3P) + H 2O → HO 2 + H reaction excitation function. Journal of Physical Chemistry A. 2007 Nov 1;111(43):10907-10913. https://doi.org/10.1021/jp0744228
Brunsvold, Amy L. ; Zhang, Jianming ; Upadhyaya, Hari P. ; Minton, Timothy K. ; Camden, Jon P. ; Paci, Jeffrey T. ; Schatz, George C. / Crossed-beams and theoretical studies of the O( 3P) + H 2O → HO 2 + H reaction excitation function. In: Journal of Physical Chemistry A. 2007 ; Vol. 111, No. 43. pp. 10907-10913.
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