Fine structure branching ratios and translational energies of O(3P j) atoms produced from collision induced intersystem crossing of O(1D) atoms

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Abstract
Collision induced intersystem crossing of O(2p 1D) to O(2p 3Pj) j=0,1,2 was studied by vacuum‐ultraviolet laser induced fluorescence. The nascent j‐branching ratios of O(3Pj) produced from collision of O(1D) with Xe, Kr, N2, CO2, and CF3H at the collision energy of 15.6, 14.7, 11.4, 13.0, and 14.4 kcal/mol are [O(3P0)]/[O(3P1)]/[O(3P2)]=(0.28±0.04)/(0.58±0.05)/1, (0.33±0.05)/(0.45±0.07)/1, (0.23±0.05)/(0.35±0.05)/1, (0.14±0.05)/(0.41±0.05)/1, and (0.20±0.05)/(0.45±0.05)/1, respectively. The j‐branching ratios are discussed in terms of potential curve crossing between singlet and triplet surfaces and nonadiabatic nature of the potential surfaces. Doppler profiles of the product O(3Pj) atoms were measured as a function of time delay between pump and probe laser pulses. By calculating the kinetic energy from the Doppler profiles, electronic energy transfer efficiencies to the internal energy of N2, CO, CO2, and CF3H are obtained to be (30±7), (31±7), (49±3), and (52±5)%, respectively.