Cold collisions between OH and Rb: The field-free case

We have calculated elastic and state-resolved inelastic cross sections for cold and ultracold collisions in the Rb(S-1)+OH((2)Pi(3/2)) system, including fine-structure and hyperfine effects. We have developed a set of five potential energy surfaces for Rb-OH (2 Pi) from high-level ab initio electronic structure calculations, which exhibit conical intersections between covalent and ion-pair states. The surfaces are transformed to a quasidiabatic representation. The collision problem is expanded in a set of channels suitable for handling the system in the presence of electric and/or magnetic fields, although we consider the zero-field limit in this work. Because of the large number of scattering channels involved, we propose and make use of suitable approximations. To account for the hyperfine structure of both collision partners in the short-range region we develop a frame-transformation procedure which includes most of the hyperfine Hamiltonian. Scattering cross sections on the order of 10(-13) cm(2) are predicted for temperatures typical of Stark decelerators. We conclude that spin orientation of the partners is completely disrupted during the collision. Implications for both sympathetic cooling of OH molecules in an environment of ultracold Rb atoms and experimental observability of the collisions are discussed.