Journal of Chemical Physics, Vol.100, No.11, 8026-8039, 1994
Differential Cross-Sections for Fine-Structure Transitions in O(P-3(2))+ar Collisions
We present experimental and theoretical differential cross sections for the fine structure changing process Ar + O((3)p(2))->Ar + O(P-3(jmj)) with (j,m(j))=(1,1), (1,0), and (0,0). rue measured cross sections refer to a collision energy of 3.2 kcal/mol, and were obtained from Doppler line shapes associated with (2+1) resonance-enhanced multiphoton ionization of O(P-3(jmj)) after scattering in a crossed-beam apparatus. The theoretical results are based on (3) Sigma(-) and (II)-I-3 potential curves obtained from high quality ab initio calculations, and on quantum coupled-channel calculations. The calculated differential cross sections show strong Stuckelberg oscillations, with similar magnitudes and phases for all three final states. With slight adjustment (0.03 Angstrom) of the hard wall on the (3) Sigma(-) curve, the calculated angular distributions match up well with the corresponding experimental results, much better than is found using previously derived empirical potentials. At the same time, the integral total cross sections obtained from the ab initio measurements are in satisfactory agreement with previous measurements.
Keywords:CORRELATED MOLECULAR CALCULATIONS;GAUSSIAN-BASIS SETS;OPEN-SHELL SYSTEMS;SCATTERING;EXCITATION;HE;ENERGY;STATES;H-2