The role of the F spin-orbit excited state in the F+H2 and F+HD reactions

Abstract

In this dissertation we study the role of the F spin-orbit excited state (F*) in the F+H2 and F+HD reactions using quantum mechanical calculations. The calculations involve multiple potential energy surfaces (the Alexander-Stark-Werner, or ASW, PESs), and include an accurate treatment of the couplings (non-adiabatic, spin-orbit, and Coriolis) among all three electronic states. For the F+H2 reaction, we calculate the center-of-mass differential cross sections and laboratory-frame angular distributions at the four different combinations of collision energies and hydrogen isotopomer investigated in the experiments of Neumark et al. [J. Chem. Phys., 82, 3045 (1985)]. Comparisons with the calculations on the Stark-Werner (SW) and Hartke-Stark-Werner (HSW) PESs, which are limited to the lowest electronically adiabatic state, show that non-adiabatic couplings greatly reduce backward scattering. Surprisingly, we find the shapes of both the CM DCSs and LAB ADs are insensitive to the fraction of F* presented in the F beam. For the F+HD reaction, we calculate the excitation functions and product translational energy distribution functions to study the reactivity of F*. Comparisons with the experiment by Liu and co-workers [J. Chem. Phys., 113, 3633 (2000)] confirm the relatively low reactivity of spin-orbit excited state (F*) atoms. Excellent agreement with the experiment is obtained under the assumption that the F*:F concentration ratio equals 0.16:0.84 in the molecular beam, which corresponds to a thermal equilibrium of the two spin-orbit states at the experimental temperature (600K). From the accurate calculation of the F* reactivity and its relatively small contribution to the overall reactivity of the reaction, we attribute discrepancies between calculation and experiment to an inadequacy in the simulation of the reactivity of the F ground state, likely a result of the residual errors in the ground electronic potential energy surface.