Journal of Chemical Physics, Vol.104, No.10, 3555-3566, 1996
State-Resolved Differential Scattering in Open-Shell Collisions - Cl(P-2(3/2))+hcl from High-Resolution Infrared-Laser Dopplerimetry
Time- and frequency-resolved IR-laser absorption methods are used to probe state-resolved collisional energy transfer in open-shell collisions of Cl(P-2(3/2)) radicals with HCl(J) in the near single-collision regime. Translationally "hot" Cl(P-2(3/2)) radicals are formed by excimer laser photolysis of Cl-2, which then collide with a room-temperature distribution of HCl peaked at J congruent to 3. Final-state distributions of the HCl are monitored via transient absorption detection of a cw IR probe laser by the collisionally populated states (J = 4, 5, 6,...,12). In previous work [J. Chem. Phys. 102, 7046 (1995)], these transient signals are used to extract absolute integral collisional cross sections for state-resolved rotational energy transfer into final J states. In the present study, high-resolution IR Dopplerimetry with the single-mode probe laser is used to measure translational distributions of the collisionally populated HCl(J) as a function of final J state. Analysis of these translational distributions leads to state-resolved differential scattering cross sections for rotational energy transfer, which exhibit a strong propensity for forward scattering into all levels observed (J less than or equal to 12). These results are compared with quasiclassical trajectory calculations (QCT) on a recently modified potential energy surface of Schatz and Gordon. The theoretical analysis is in good agreement with experiment, with the angular distribution dominated by forward scattering for most of the final HCl rotational states. However, for the very highest J states collisionally populated, the QCT calculations predict a shift from predominantly forward to more isotropic scattering that is not evident in the experimental results.
Keywords:ROTATIONALLY INELASTIC-SCATTERING;CROSS-SECTIONS;TRANSITION-STATE;ENERGY-DISTRIBUTIONS;CHEMICAL-REACTIONS;CHLORINE ATOMS;QUANTUM;DYNAMICS;AR;PHOTODISSOCIATION