Hyperthermal reactions of O +( 4S 3/2) with CD 4 and CH 4: Theory and experiment

Dale J. Levandier, Yu Hui Chiu, Rainer A. Dressler, Lipeng Sun, George C Schatz

Research output: Contribution to journalArticle

16 Citations (Scopus)

Abstract

Theoretical and experimental methods are applied to the study of the reaction dynamics in hyperthermal collisions of O + ( 4S 3/2) with methane. Measurements of the absolute reaction cross sections for the interaction of O + with CD 4 and CH 4 were obtained at collision energies in the range from near-thermal to approximately 15 eV, using the guided-ion beam (GIB) technique. Product recoil velocity distributions, using the GIB time-of-flight (TOF) methods, were determined for several product ions at selected collision energies. The main reaction channel, charge transfer, proceeds via large impact parameter collisions. A number of minor channels, involving more intimate collisions, were also detected. Ab initio electronic structure calculations have been performed with different levels of theory and basis sets, including high-level coupled-cluster calculations to determine the energies of reaction intermediates and transition states for reaction. Several reaction paths on both quartet and doublet electronic states of (O·CH 4) + are found, and these provide a reasonable qualitative interpretation of the experiments. Although most of the products can be produced via spin-allowed pathways, the appearance of CH 3 + at low energies suggests that intersystem crossing plays some role.

Original languageEnglish
Pages (from-to)9794-9804
Number of pages11
JournalJournal of Physical Chemistry A
Volume108
Issue number45
DOIs
Publication statusPublished - Nov 11 2004

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Ion beams
methylidyne
Reaction intermediates
Methane
Electronic states
Velocity distribution
collisions
Electronic structure
Charge transfer
Experiments
Ions
products
ion beams
collision parameters
reaction intermediates
energy
methane
velocity distribution
charge transfer
electronic structure

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry

Cite this

Hyperthermal reactions of O +( 4S 3/2) with CD 4 and CH 4 : Theory and experiment. / Levandier, Dale J.; Chiu, Yu Hui; Dressler, Rainer A.; Sun, Lipeng; Schatz, George C.

In: Journal of Physical Chemistry A, Vol. 108, No. 45, 11.11.2004, p. 9794-9804.

Research output: Contribution to journalArticle

Levandier, Dale J. ; Chiu, Yu Hui ; Dressler, Rainer A. ; Sun, Lipeng ; Schatz, George C. / Hyperthermal reactions of O +( 4S 3/2) with CD 4 and CH 4 : Theory and experiment. In: Journal of Physical Chemistry A. 2004 ; Vol. 108, No. 45. pp. 9794-9804.
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