Reaction dynamics study of O{sup -}+C{sub 2}H{sub 2} with crossed beams and density-functional theory calculations

Journal Article · Thu Sep 01 04:00:00 EDT 2005 · Journal of Chemical Physics

DOI:https://doi.org/10.1063/1.2000947· OSTI ID:20723041

Li, Liu; Yue, Li; Farrar, James M ^[1]

---

1. Department of Chemistry, University of Rochester, Rochester, New York 14627 (United States)

The reactions between O{sup -} and C{sub 2}H{sub 2} have been studied using the crossed-beam technique and density-functional theory (DFT) calculations in the collision energy range from 0.35 to 1.5 eV (34-145 kJ/mol). Both proton transfer and C-O bond formation are observed. The proton transfer channel forming C{sub 2}H{sup -} is the dominant pathway. The center-of-mass flux distributions of the C{sub 2}H{sup -} product ions are highly asymmetric, with maxima close to the velocity and direction of the precursor acetylene beam, characteristic of direct reactions. The reaction quantitatively transforms the entire reaction exothermicity into internal excitation of the products, consistent with mixed energy release in which the proton is transferred in a configuration in which both the breaking and the forming bonds are extended. The C-O bond formation channel producing HC{sub 2}O{sup -} displays a distinctive kinematic picture in which the product distribution switches from predominantly forward scattering with a weak backward peak to sideways scattering as the collision energy increases. At low collision energies, the reaction occurs through an intermediate that lives a significant fraction of a rotational period. The asymmetry in the distribution leads to a lifetime estimate of 600 fs, in reasonable agreement with DFT calculations showing that hydrogen-atom migration is rate limiting. At higher collision energies, the sideways-scattered products arise from repulsive energy release from a bent transition state.

• OSTI ID: 20723041
• Journal Information: Journal of Chemical Physics, Journal Name: Journal of Chemical Physics Journal Issue: 9 Vol. 123; ISSN JCPSA6; ISSN 0021-9606
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
ACETYLENE
CENTER-OF-MASS SYSTEM
CHEMICAL BONDS
COLLIDING BEAMS
DENSITY FUNCTIONAL METHOD
DIRECT REACTIONS
EV RANGE 01-10
EXCITATION
HYDROGEN
ION-MOLECULE COLLISIONS
MILLI EV RANGE
OXYGEN
OXYGEN IONS
REACTION KINETICS