title: Experimental and theoretical studies of the O(3P) + C2H4 reaction dynamics: collision energy dependence of branching ratios and extent of intersystem crossing.
abstract: The reaction of O((3)P) with C(2)H(4), of importance in combustion and atmospheric chemistry, stands out as paradigm reaction involving not only the indicated triplet state potential energy surface (PES) but also an interleaved singlet PES that is coupled to the triplet surface. This reaction poses great challenges for theory and experiment, owing to the ruggedness and high dimensionality of these potentials, as well as the long lifetimes of the collision complexes. Crossed molecular beam (CMB) scattering experiments with soft electron ionization detection are used to disentangle the dynamics of this polyatomic multichannel reaction at a collision energy E(c) of 8.4 kcal∕mol. Five different primary products have been identified and characterized, which correspond to the five exothermic competing channels leading to H + CH(2)CHO, H + CH(3)CO, CH(3) + HCO, CH(2) + H(2)CO, and H(2) + CH(2)CO. These experiments extend our previous CMB work at higher collision energy (E(c) ∼ 13 kcal∕mol) and when the results are combined with the literature branching ratios from kinetics experiments at room temperature (E(c) ∼ 1 kcal∕mol), permit to explore the variation of the branching ratios over a wide range of collision energies. In a synergistic fashion, full-dimensional, QCT surface hopping calculations of the O((3)P) + C(2)H(4) reaction using ab initio PESs for the singlet and triplet states and their coupling, are reported at collision energies corresponding to the CMB and the kinetics ones. Both theory and experiment find almost an equal contribution from the triplet and singlet surfaces to the reaction, as seen from the collision energy dependence of branching ratios of product channels and extent of intersystem crossing (ISC). Further detailed comparisons at the level of angular distributions and translational energy distributions are made between theory and experiment for the three primary radical channel products, H + CH(2)CHO, CH(3) + HCO, and CH(2) + H(2)CO. The very good agreement between theory and experiment indicates that QCT surface-hopping calculations, using reliable coupled multidimensional PESs, can yield accurate dynamical information for polyatomic multichannel reactions in which ISC plays an important role.
authors.affiliation: Department of Chemistry and Cherry L. Emerson Center for Scientific Computation, Emory University, Atlanta, Georgia 30322, USA.
authors.forename: Bina
authors.initials: B
authors.lastname: Fu
authors.forename: Yong-Chang
authors.initials: YC
authors.lastname: Han
authors.forename: Joel M
authors.initials: JM
authors.lastname: Bowman
authors.forename: Francesca
authors.initials: F
authors.lastname: Leonori
authors.forename: Nadia
authors.initials: N
authors.lastname: Balucani
authors.forename: Luca
authors.initials: L
authors.lastname: Angelucci
authors.forename: Angela
authors.initials: A
authors.lastname: Occhiogrosso
authors.forename: Raffaele
authors.initials: R
authors.lastname: Petrucci
authors.forename: Piergiorgio
authors.initials: P
authors.lastname: Casavecchia