Cold Collisions of Ro-Vibrationally Excited D 2 Molecules.

The H 2 + H 2 system has long been considered a benchmark system for ro-vibrational energy transfer in bimolecular collisions. However, most studies thus far have focused on collisions involving H 2 molecules in the ground vibrational level or in the first excited vibrational state. While H 2 + H 2 /HD collisions have received wide attention due to the important role they play in astrophysics, D 2 + D 2 collisions have received much less attention. Recently, Zhou et al. [ Nat. Chem. 2022, 14, 658-663, DOI: 10.1038/s41557-022-00926-z] examined stereodynamic aspects of rotational energy transfer in collisions of two aligned D 2 molecules prepared in the v = 2 vibrational level and j = 2 rotational level. Here, we report quantum calculations of rotational and vibrational energy transfer in collisions of two D 2 molecules prepared in vibrational levels up to v = 2 and identify key resonance features that contribute to the angular distribution in the experimental results of Zhou et al. The quantum scattering calculations were performed in full dimensionality and using the rigid-rotor approximation using a recently developed highly accurate six-dimensional potential energy surface for the H 4 system that allows descriptions of collisions involving highly vibrationally excited H 2 and its isotopologues.