The role of rotation in the vibrational relaxation of water by hydrogen molecules

Alexandre Faure (1) , Laurent Wiesenfeld (1) , Michael Wernli (1) , Pierre Valiron (1)

1 LAOG - Laboratoire d'Astrophysique de Grenoble

Vibrational relaxation cross sections of the H2O(υ2=1) bending mode by H2 molecules are calculated on a recent high-accuracy ab initio potential-energy surface using quasiclassical trajectory calculations. The role of molecular rotation is investigated at a collisional energy of 3500 cm-1 and it is shown that initial rotational excitation significantly enhances the total (rotationally summed) vibrational relaxation cross sections. A strong and complex dependence on the orientation of the water angular momentum is also observed, suggesting the key role played by the asymmetry of water. Despite the intrinsic limitations of classical mechanics, these exploratory results suggest that quantum approximations based on a complete decoupling of rotation and vibration, such as the widely used vibrational close-coupling (rotational) infinite-order-sudden method, would significantly underestimate rovibrationally inelastic cross sections. We also present some rationale for the absence of dynamical chaos in the scattering process.

Alexandre Faure, Laurent Wiesenfeld, Michael Wernli, Pierre Valiron. The role of rotation in the vibrational relaxation of water by hydrogen molecules. Journal of Chemical Physics, 2005, 123, pp.104309. ⟨10.1063/1.2033767⟩. ⟨hal-00398172⟩