Spin-orbit relaxation of Cl(P-2(1/2)) and F(P-2(1/2)) in a gas of H-2

The authors present quantum scattering calculations of rate coefficients for the spin-orbit relaxation of F(P-2(1/2)) atoms in a gas of H-2 molecules and Cl(P-2(1/2)) atoms in a gas of H-2 and D-2 molecules. Their calculation of the thermally averaged rate coefficient for the electronic relaxation of chlorine in H-2 agrees very well with an experimental measurement at room temperature. It is found that the spin-orbit relaxation of chlorine atoms in collisions with hydrogen molecules in the rotationally excited state j = 2 is dominated by the near-resonant electronic-to-rotational energy transfer accompanied by rotational excitation of the molecules. The rate of the spin-orbit relaxation in collisions with D-2 molecules increases to a great extent with the rotational excitation of the molecules. They have found that the H-2/D-2 isotope effect in the relaxation of Cl(P-2(1/2)) is very sensitive to temperature due to the significant role of molecular rotations in the nonadiabatic transitions. Their calculation yields a rate ratio of 10 for the electronic relaxation in H-2 and D-2 at room temperature, in qualitative agreement with the experimental measurement of the isotope ratio of about 5. The isotope effect becomes less significant at higher temperatures. (c) 2007 American Institute of Physics.