title: The reaction OH + C2H4: an example of rotational channel switching.
abstract: The low-temperature data for the reaction between OH and C(2)H(4) is treated canonically as either a two-well or one-well problem using the "Multiwell" suite of codes, in which a "well" refers to a minimum in the potential energy surface. The former is analogous to the two transition state model of Greenwald et al. [Greenwald, E. E.; North, S. W.; Georgievskii, Y.; Klippenstein, S. J. J. Phys. Chem. A2005, 109, 6031], while the latter reflects the dominance of the so-called "inner transition state". External rotations are treated adiabatically, causing changes in the magnitude of effective barriers as a function of temperature. Extant data are well-described with either model using only the average energy transferred in a downward direction, upon collision, ΔE(d)(T), as a fitting parameter. The best value for the parameters describing the rate coefficient as a function of temperature (200 < T/K < 400) (Data at lower temperature is too sparse to yield a recommendation.) and pressure in the form used in the NASA/JPL format [Sander, S. P.; Abbatt, J.; Barker, J. R.; Burkholder, J. B.; Friedl, R. R.; Golden, D. M.; Huie, R. E.; Kolb, C. E.; Kurylo, M. J.; Moortgat, G. K et al., Chemical Kinetics and Photochemical Data for Use in Atmospheric Studies, Evaluation Number 17, Jet Propulsion Laboratory, 2011] are k(0) = 1.0 × 10(-28)(T/300)(-3.5) cm(6) molecule(-2) s(-1) and k(∞) to 8.0 × 10(-12)(T/300)(-2.3) cm(3) molecule(-1) s(-1).
authors.affiliation: Department of Mechanical Engineering, Stanford University, Stanford, California 94305, USA.
authors.forename: David M
authors.initials: DM
authors.lastname: Golden