Classical theory of rotational rainbow scattering from uncorrugated surfaces

A classical perturbation theory is developed to study rotational rainbow scattering of molecules from uncorrugated frozen surfaces. Considering the interaction of the rigid rotor with the translational motion towards the surface to be weak allows for a perturbative treatment, in which the known zeroth order motion is that of a freely rotating molecule hitting a surface. Using perturbation theory leads to explicit expressions for the angular momentum deflection function with respect to the initial orientational angle of the rotor that are valid for any magnitude of the initial angular momentum. The rotational rainbows appear as peaks both in the final angular momentum and rotational energy distributions, as well as peaks in the angular distribution, although the surface is assumed to be uncorrugated. The derived analytic expressions are compared with numerical simulation data. Even when the rotational motion is significantly coupled to the translational motion, the predictions of the perturbative treatment remain qualitatively correct.