Tensor cross sections and the collisional evolution of state multipoles: OH(X 2Π)-Ar

By means of a kinetic analysis, we show that the overall rate constant for the collisional loss of orientation or alignment of a rotational level is the sum of the rate constant for elastic depolarization and the sum of the rate constants for all rotationally inelastic transitions out of the level under consideration. An expression for the depolarization cross section is derived in terms of tensor cross sections, and the relationship of depolarization to m-resolved transitions is discussed. We use this formalism in simulations, based on high-quality ab initio potential energy surfaces, of the depolarization of the open-shell molecule OH(X (2)Pi) through collisions with Ar. Good agreement is seen with the results of the two-color polarization spectroscopy experiments of Paterson [J. Chem. Phys. 129, 074304 (2008)]. In addition, we show that the major contribution to elastic collisional depolarization occurs not from weak, glancing collisions but from encounters which probe the inner wall of the potential energy surface.