Rotationally inelastic scattering of jet cooled H2O with Ar: State-to-state cross sections and rotational alignment effects

State-to-state rotationally inelastic scattering cross sections of ${\mathrm{H}}_{\mathrm{2}}\mathrm{O}$ with Ar are measured under single-collision conditions in crossed supersonic jets at a collision energy of 480(90) cm⁻¹. The ${\mathrm{H}}_{\mathrm{2}}\mathrm{O}$ is initially prepared in its lowest ortho ${\text{(1}}_{01})$ and para ${\text{(0}}_{00})$ 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 ${\mathrm{H}}_{\mathrm{2}}\mathrm{O}$ in both initial and final scattering states are monitored via direct absorption of narrow bandwidth $\text{(Δν≈0.0001\hspace{0.05em}}{\mathrm{cm}}^{\mathrm{-1}})$ 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 ${\mathrm{Ar-H}}_{\mathrm{2}}\mathrm{O}$ 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.