Stereodynamic descriptions of molecular collisions concern the angular correlations that exist between vector properties of the motion of the participating species, including their velocities and rotational angular momenta. Measurements of vector correlations provide a unique view of the forces acting during collisions, and are a stringent test of electronic-structure calculations of molecular interactions. Here, we present direct measurement of the four-vector correlation between initial and final relative velocities and rotational angular momenta in a molecular collision. This property, which quantifies the extent to which a molecule retains a memory of its initial sense of rotation, or handedness, as a function of scattering angle, yields insight into the dynamics of a molecular collision. We report non-intuitive changes in the handedness for specific states and scattering angles, reproduced by classical and quantum scattering calculations. Comparison to calculations on different ab initio potential energy surfaces demonstrates this measurement's exquisite sensitivity to the underlying intermolecular forces.

Crossed molecular beam scattering and quantum scattering calculations reveal the dynamical mechanisms underlying rotationally inelastic scattering for NO(A) + Kr.

The ability of gas-surface dynamics studies to resolve the velocity distribution of the scattered species in the 2D scattering plane has been limited by technical capabilities and only a few different approaches have been explored in recent years. In comparison, gas-phase scattering studies have been transformed by the near ubiquitous use of velocity map imaging. We describe an innovative means of introducing a dielectric surface within the electric field of a typical velocity map imaging experiment. The retention of optimum velocity mapping conditions was validated by measurements of iodomethane-d photodissociation and SIMION calculations. To demonstrate the system's capabilities, the velocity distributions of ammonia molecules scattered from a polytetrafluoroethylene surface have been measured for multiple product rotational states.

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