Abstract
The nonadiabatic close-coupled theory of atomic collisions in a radiation field is generalized to include electron spin and is used to consider the weak-field Na--rare-gas (RG) optical collision Na${(}^{2}$${S}_{1/2}$)+RG+nh\ensuremath{\nu} \ensuremath{\mu}Na${(}^{2}$${\mathrm{P}}_{\mathrm{j}}$)+RG+(n-1)h\ensuremath{\nu}. The effects of detuning and incident energy on the branching into the atomic Na 3${p}^{2}$${P}_{3/2}$ and 3p $^{2}P_{1/2}$ states are examined. The cross sections \ensuremath{\sigma}(j) are found to have a strong asymmetry between red and blue detuning as well as a complex threshold and resonance structure dependence on energy. A partial cross-section analysis of \ensuremath{\sigma}(j) shows a significant difference between contributions from states of e and f molecular parity. The theoretically calculated detuning dependence of the branching ratio into each fine-structure state is in good agreement with available experimental data for Na-Ar, Na-Ne, and Na-He, as well as the total absorption coefficient for the production of Na 3p atoms. The fine-structure branching ratio for thermal energy collisions shows considerable variation with a rare-gas collision partner, due to the different interaction potentials. For sufficiently high collision energy, the branching approaches a recoil limit which is independent of collision partner.
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