Journal of Chemical Physics, Vol.106, No.18, 7642-7653, 1997
Inelastic-Collisions of Fine-Structure and Lambda-Doublet Resolved Rotational States of pH(A (3)Pi, V=0) with Helium
A state-resolved experimental and theoretical investigation of inelastic collisions of PII(A (II)-I-3) rotational/fine-structure levels with helium is presented. Experimental stare-to-stale rate constants were extracted from PH A-->X fluorescence spectra recorded upon laser excitation to individual levels in the A state in the presence of helium. These rate constants have been compared with and interpreted through theoretical rate constants computed with full quantum close-coupling and coupled-states calculations of cross sections based on ab initio PK(A)-He potential energy surfaces determined by Kolczewski ct al. [J. Chem. Phys. 106, 7637 (1997)]. The low-J rotational levels of PI-I(A) are close to the Hund’s case (a) limit, and the cross sections exhibit a number of the predicted case (a) collisional propensities. For low initial N, there is a strong propensity for fine-structure conserving transitions. With increasing initial N, fine-structure changing transitions occur with increasing probability. This tendency appears to be related to the transition of the coupling scheme away from pure case (a).
Keywords:FOURIER-TRANSFORM SPECTROSCOPY;POTENTIAL-ENERGY SURFACES;DIATOMIC-MOLECULES;ELECTRONIC STATES;PROPENSITY RULES;NA2B(3)PI(U) STATE;RELAXATION;QUANTUM;SCATTERING;SPIN