Rotationally inelastic scattering of jet cooled H_2O with Ar: State-to-state cross sections and rotational alignment effects

摘要

State-to-state rotationally inelastic scattering cross sections of H_2O with Ar are measured under single-collision conditions in crossed supersonic jets at a collision energy of 480(90) cm~(-1). The H_2O is initially prepared in its lowest ortho (1_(01)) and para (0_(00)) rotational levels by supersonic cooling in a Ne expansion, and then excited in the intersection region by single collisions with a second pulsed jet of Ar atoms. Column-integrated densities of H_2O in both initial and final scattering states are monitored via direct absorption of narrow bandwidth (#DELTA#v approx= 0.0001 cm~(-1)) infrared light from a continuous wave (cw) F-center laser. Absolute inelastic cross sections for state-to-state collisional energy transfer out of para and ortho initial states are determined from the dependence of infrared absorption signals on collider gas densities. Overall, the results can be approximately characterized by an exponential decrease in cross section with the magnitude of rotational energy transferred, i.e., as suggested by exponential energy gap models. However, at the state-to-state level, a highly structured, nonmonotonic dependence on energy is observed, which indicates a propensity for rotational excitation around the A (in-plane, perpendicular to C_2) and C (out-of-plane) principal axes. This preferential state-to-state scattering dynamics reflects an intramolecular alignment of J in the body-fixed frame and is in good qualitative agreement with theoretical classical trajectory predictions. A rigorous comparison is made via full quantum close-coupling scattering calculations on empirical and ab initio Ar-H_2O potential energy surfaces, which successfully reproduce all the state-to-state trends observed, but at the more quantitative level appear to overestimate the intramolecular alignment effects experimentally observed.