Quantum-State-Resolved CO2 Scattering Dynamics at the Gas−Liquid Interface: Incident Collision Energy and Liquid Dependence

Abstract

Quantum-state-resolved dynamics at the gas-liquid interface are probed by colliding supersonically cooled molecular beams of CO(2) with freshly formed liquid surfaces in a vacuum. Translational, rotational, and vibrational state distributions of both incident and scattered fluxes are measured by high-resolution direct infrared absorption spectroscopy and laser dopplerimetry in the 00(0)0 and 01(1)0 rovibrational manifolds of CO(2) in the asymmetric stretch manifold. The present studies investigate the role of incident molecular beam energy (E(inc) = 1.6(1), 4.7(2), 7.7(2), and 10.6(8) kcal/mol) on these distributions for a series of perfluorinated, hydrocarbon, and hydrogen-bonded liquids. Boltzmann analysis of the internal quantum-state populations provide evidence for nonthermal scattering dynamics, as confirmed by Dopplerimetry on the absorption profiles. The data provide quantum-state-resolved support for a dual channel picture of the scattering process, consisting of either prompt impulsive scattering (IS) or longer duration trapping-desorption (TD) events, with the fraction observed in each channel dependent on incident kinetic energy and the physical properties of the liquid surface. The clear evidence that internal CO(2) rotational populations arising from the IS channel can be adequately described by a Boltzmann temperature (albeit with E(IS) > RT(S)) is consistent with previous gas-solid scattering studies and suggests that even nominally "prompt" IS events reflect both single (i.e. direct) and multiple impulsive interactions with the liquid interface.