title: An improved potential energy surface and multi-temperature quasiclassical trajectory calculations of N2 + N2 dissociation reactions.
abstract: Accurate modeling of high-temperature hypersonic flows in the atmosphere requires consideration of collision-induced dissociation of molecular species and energy transfer between the translational and internal modes of the gas molecules. Here, we describe a study of the N2 + N2⟶N2 + 2N and N2 + N2⟶4N nitrogen dissociation reactions using the quasiclassical trajectory (QCT) method. The simulations used a new potential energy surface for the N4 system; the surface is an improved version of one that was presented previously. In the QCT calculations, initial conditions were determined based on a two-temperature model that approximately separates the translational-rotational temperature from the vibrational temperature of the N2 diatoms. Five values from 8000 K to 30,000 K were considered for each of the two temperatures. Over 2.4 × 10(9) trajectories were calculated. We present results for ensemble-averaged dissociation rate constants as functions of the translational-rotational temperature T and the vibrational temperature T(v). The rate constant depends more strongly on T when T(v) is low, and it depends more strongly on T(v) when T is low. Quasibound reactant states contribute significantly to the rate constants, as do exchange processes at higher temperatures. We discuss two sets of runs in detail: an equilibrium test set in which T = T(v) and a nonequilibrium test set in which T(v) < T. In the equilibrium test set, high-v and moderately-low-j molecules contribute most significantly to the overall dissociation rate, and this state specificity becomes stronger as the temperature decreases. Dissociating trajectories tend to result in a major loss of vibrational energy and a minor loss of rotational energy. In the nonequilibrium test set, as T(v) decreases while T is fixed, higher-j molecules contribute more significantly to the dissociation rate, dissociating trajectories tend to result in a greater rotational energy loss, and the dissociation probability's dependence on v weakens. In this way, as T(v) decreases, rotational energy appears to compensate for the decline in average vibrational energy in promoting dissociation. In both the equilibrium and nonequilibrium test sets, in every case, the average total internal energy loss in the dissociating trajectories is between 10.2 and 11.0 eV, slightly larger than the equilibrium potential energy change of N2 dissociation.
authors.affiliation: Department of Aerospace Engineering and Mechanics, University of Minnesota, Minneapolis, Minnesota 55455, USA.
authors.forename: Jason D
authors.initials: JD
authors.lastname: Bender
authors.affiliation: Department of Aerospace Engineering and Mechanics, University of Minnesota, Minneapolis, Minnesota 55455, USA.
authors.forename: Paolo
authors.initials: P
authors.lastname: Valentini
authors.affiliation: Department of Aerospace Engineering and Mechanics, University of Minnesota, Minneapolis, Minnesota 55455, USA.
authors.forename: Ioannis
authors.initials: I
authors.lastname: Nompelis
authors.affiliation: Department of Chemistry, Chemical Theory Center, and Supercomputing Institute, University of Minnesota, Minneapolis, Minnesota 55455, USA.
authors.forename: Yuliya
authors.initials: Y
authors.lastname: Paukku
authors.affiliation: Department of Chemistry, Chemical Theory Center, and Supercomputing Institute, University of Minnesota, Minneapolis, Minnesota 55455, USA.
authors.forename: Zoltan
authors.initials: Z
authors.lastname: Varga
authors.affiliation: Department of Chemistry, Chemical Theory Center, and Supercomputing Institute, University of Minnesota, Minneapolis, Minnesota 55455, USA.
authors.forename: Donald G
authors.initials: DG
authors.lastname: Truhlar
authors.affiliation: Department of Aerospace Engineering and Mechanics, University of Minnesota, Minneapolis, Minnesota 55455, USA.
authors.forename: Thomas
authors.initials: T
authors.lastname: Schwartzentruber
authors.affiliation: Department of Aerospace Engineering and Mechanics, University of Minnesota, Minneapolis, Minnesota 55455, USA.
authors.forename: Graham V
authors.initials: GV
authors.lastname: Candler