Comparison of close-coupling and approximate methods for F( 2P [formula omitted]) + H 2 non-reactive collisions: Translational wavefunction analysis

Abstract

Electronic-rotational energy transfer in F( 2P 1 2 ) + H 2 ( j = 0) non-reactive collisions is studied by analyzing the translational wavefunctions (TW) and transition probabilities of four model problems: full close-coupling (CC), diabatic (DDW) and adiabatic (ADW) distorted-wave Born theories, and an asymptotic sine-wave model. Comparisons among the approximate models are discussed and their accuracy is examined. DIM theory provides the diabatic electronic matrix elements, and the close-coupled equations are solved by the R-matrix method. The resulting S-matrix elements times their appropriate asymptotic wavefunctions when propagated in along the reaction coordinate generate the TW. For the CC results, relations between the TW and the adiabatic electrotational energy correlation diagrams are emphasized, while for the other models the effects of classical turning points, diabatic energy level structure, unitarization techniques, and other dynamical factors on the state-to-state transition probabilities are examined.