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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-D2O by ground-state para-H2 in the threshold region of the D2O(000→202) 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 D2O-H2 intermolecular potential. Our theoretical cross section 000→202 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. [ABSTRACT FROM AUTHOR]

We report integral cross sections for the S(1D2)+HD(j=0)→DS+H and HS+D reaction channels obtained through crossed-beam experiments reaching collision energies as low as 0.46 meV and from adiabatic time-independent quantum-mechanical calculations. While good overall agreement with experiment at energies above 10 meV is observed, neither the product channel branching ratio nor the low-energy resonancelike features in the HS+D channel can be theoretically reproduced. A nonadiabatic treatment employing highly accurate singlet and triplet potential energy surfaces is clearly needed to resolve the complex nature of the reaction dynamics.

We report on crossed-beam experiments and quantum-mechanical calculations performed on the CO(j=0) + H2(j=0) → CO(j=1) + H2(j=0) system. The experimental cross sections determined in the threshold region of the CO(j=0 → j=1) transition at 3.85  cm(-1) show resonance structures in good qualitative agreement with the theoretical ones. These results suggest that the potential energy surface which describes the CO-H2 van der Waals interaction should be reinvestigated for good quantitative agreement.

We report combined studies on the prototypical S(1D2) + H2 insertion reaction. Kinetics and crossed-beam experiments are performed in experimental conditions approaching the cold energy regime, yielding absolute rate coefficients down to 5.8 K and relative integral cross sections to collision energies as low as 0.68 meV. They are supported by quantum calculations on a potential energy surface treating long-range interactions accurately. All results are consistent and the excitation function behavior is explained in terms of the cumulative contribution of various partial waves.