Pseudo-Quenching Model Studies of Spin-Orbit State Propensities in Reactions of Ca(4s4p(3)p) with C1(2)

摘要

A pseudo-quenching model is developed to investigate the dependence on initial spin-orbit state of the Ca(4s4p3p) + Cl2 reactive cross sections. The ionic diabatic is restricted to couple directly to only one of the two covalent curves. At somewhat closer distances the ionic curve is crossed by, and adiabatically mixed with, another repulsive curve which correlates with a lower energy asymptote, to mimic the exoergic reaction. Within this model the collision dynamics are treated fully quantum mechanically; the coupling arising from the spin-orbit, rotational, and electrostatic Hamiltonians is included without approximation. The vibration of the cross sections with the choice of the parameters which describe the various diabatic potentials illustrates (1) an extreme sensitivity to the strength to the ionic-covalent coupling and (2) the qualitative validity of simple adiabatic correlation arguments even in this weak spin-orbit coupling limit.