Quantum state-resolved CO2 collisions at the gas-liquid interface: surface temperature-dependent scattering dynamics.

Energy transfer dynamics at the gas-liquid interface are investigated as a function of surface temperature both by experimental studies of CO2 + perfluorinated polyether (PFPE) and by molecular dynamics simulations of CO2 + fluorinated self-assembled monolayers (F-SAMs). Using a normal incident molecular beam, the experimental studies probe scattered CO2 internal-state and translational distributions with high resolution infrared spectroscopy. At low incident energies [Einc = 1.6(1) kcal/mol], CO2 J-state populations and transverse Doppler velocity distributions are characteristic of the surface temperature (Trot approximately Ttrans approximately TS) over the range from 232 to 323 K. In contrast, the rotational and translational distributions at high incident energies [Einc = 10.6(8) kcal/mol] show evidence for both trapping-desorption (TD) and impulsive scattering (IS) events. Specifically, the populations are surprisingly well-characterized by a sum of Boltzmann distributions where the two components include one (TD) that equilibrates with the surface (TTD approximately TS) and a second (IS) that is much hotter than the surface temperature (TIS > TS). Support for the superthermal, yet Boltzmann, nature of the IS channel is provided by molecular dynamics (MD) simulations of CO2 + F-SAMs [Einc = 10.6 kcal/mol], which reveal two-temperature distributions, sticking probabilities, and angular distributions in near quantitative agreement with the experimental PFPE results. Finally, experiments as a function of surface temperature reveal an increase in both sticking probability and rotational/translational temperature of the IS component. Such a trend is consistent with increased surface roughness at higher surface temperature, which increases the overall probability of trapping, yet preferentially leads to impulsive scattering of more highly internally excited CO2 from the surface.