Quantum state resolved velocity-map imaging spectroscopy: A new tool for collision dynamics at gas/self-assembled monolayer interfaces

Abstract

The dynamics of HCl scattering from a room-temperature –CH₃ terminated self-assembled monolayer (SAM) is probed via state-resolved spectroscopy coupled to a velocity-map imaging (VMI) apparatus. The resulting velocity maps provide new insight into the HCl scattering trajectories, revealing for the first time correlations between internal and translational degrees of freedom. Velocity maps at low J are dominated by signatures of both the incident beam (17.3(3) kcal mol⁻¹) and a room-temperature trapping–desorption component (TD). At high J, however, the maps contain a large, continuous feature associated primarily with impulsive scattering (IS). Trajectories resulting from these strongly inelastic interactions are readily isolated in the map, and provide a new glimpse into purely impulsive scattering dynamics. Specifically, within the purely-IS HCl region of the velocity maps, the rotational distribution is found to be remarkably Boltzmann like, but with a temperature (472 K) significantly higher than the SAM surface (300 K). By way of contrast, the translational degree of freedom of the impulsively-scattered flux is clearly non-Boltzmann in character, with a strong propensity for in-plane scattering in the forward direction, and yet still exhibiting out-of-plane velocity distributions reasonably well characterized by a temperature of 690 K. These first data establish the prospects for a new class of experimental tools aimed at exploring energy transfer and reactive scattering events on SAMs, liquid, and metal interfaces with quantum state resolved information on correlated internal and translational distributions.