Probing Low-Energy Resonances in Water-Hydrogen Inelastic Collisions.

Molecular scattering at collisional energies of the order of 10-100 cm^{-1} (corresponding to kinetic temperatures in the 15-150 K range) provides insight into the details of the scattering process and, in particular, of the various resonances that appear in inelastic cross sections. In this Letter, we present a detailed experimental and theoretical study of the rotationally inelastic scattering of ground-state ortho-D_{2}O by ground-state para-H_{2} in the threshold region of the D_{2}O(0_{00}→2_{02}) transition at 35.9 cm^{-1}. The measurements were performed with a molecular crossed beam apparatus with variable collision angle, thence with variable collisional energy. Calculations were carried out with the coupled-channel method combined with a dedicated high-level D_{2}O-H_{2} intermolecular potential. Our theoretical cross section 0_{00}→2_{02} is found to display several resonance peaks in perfect agreement with the experimental work, in their absolute positions and relative intensities. We show that those peaks are mostly due to shape resonances, characterized here for the first time for a polyatomic molecule colliding with a diatom.

Comparative experimental and theoretical study of the rotational excitation of CO by collision with ortho- and para-D2 molecules.

A joint crossed beam and quantum mechanical investigation of the rotationally inelastic collisions of CO with ortho- and para-D2 molecules is reported. A new 4D potential energy surface (PES) averaged over the ground vibrational states of D2 and CO is used to calculate the rovibrational bound states of the ortho-D2-CO complexes. Close coupling calculations are then performed in the rigid rotor approximation for ortho- and para-D2 colliding with CO for the experimentally investigated transition of CO (j = 0 → 1) and for collision energies ranging from 0.1 to 25 cm-1. The agreement between theory and experiment is found to be very good for both the bound state energies of the ortho-D2-CO complexes and for the inelastic scattering cross-sections showing that the free rotation of two rigid rotors is a very good model of the D2-CO system in this low collision energy domain.