Dependence of elastic depolarization cross sections on the potential: OH(X 2Pi)-Ar and NO(X 2Pi)-Ar.
Elastic tensor and depolarization cross sections are computed for the collision of two exemplary diatomic molecules with (2)Pi electronic ground states-OH and NO-with argon. The interaction of a diatomic molecule in a Pi state with a spherical collision partner must be described by two potential energy surfaces (PESs), corresponding to the two asymptotically degenerate electronic states, of A(') and A(") symmetry. Quantum scattering calculations are most naturally based on the average (V(sum)) and half-difference (V(dif)) of these two PESs. When V(dif) is neglected, the OH(X (2)Pi)-Ar depolarization cross sections are found to be significantly reduced in magnitude, while the NO(X (2)Pi)-Ar cross sections are relatively unaffected. In addition, treating the molecules as closed-shell (1)Sigma(+) species with a corresponding rotational level structure and using (V(sum)) to model the PES, we predict depolarization cross sections which differ significantly from those based on full inclusion of the electronic degeneracy and fine structure of these (2)Pi molecules. This indicates that any single-PES-based simulation of the collisional depolarization of these two molecules would be subject to significant error.
Dagdigian
Paul J
PJ
Department of Chemistry, The Johns Hopkins University, Baltimore, Maryland 21218-2685, USA. pjdagdigian@jhu.edu
Alexander
Millard H
MH