Water uptake on aerosol and cloud particles in the atmosphere modifies their chemistry and microphysics with important implications for climate on Earth. Here, we apply an environmental molecular beam (EMB) method to characterize water accommodation on ice and organic surfaces. The adsorption of surface-active compounds including short-chain alcohols, nitric acid, and acetic acid significantly affects accommodation of D2O on ice. n-Hexanol and n-butanol adlayers reduce water uptake by facilitating rapid desorption and function as inefficient barriers for accommodation as well as desorption of water, while the effect of adsorbed methanol is small. Water accommodation is close to unity on nitric-acid- and acetic-acid-covered ice, and accommodation is significantly more efficient than that on the bare ice surface. Water uptake is inefficient on solid alcohols and acetic acid but strongly enhanced on liquid phases including a quasi-liquid layer on solid n-butanol. The EMB method provides unique information on accommodation and rapid kinetics on volatile surfaces, and these studies suggest that adsorbed organic and acidic compounds need to be taken into account when describing water at environmental interfaces.

The scattering, fast and slow desorption of water molecules from solid and liquid butanol surfaces are investigated by experiments and simulations.

Water and organics are omnipresent in the atmosphere, and their interactions influence the properties and lifetime of both aerosols and clouds. Nopinone is one of the major reaction products formed from β-pinene oxidation, a compound emitted by coniferous trees, and it has been found in both gas and particle phases in the atmosphere. Here, we investigate the interactions between water molecules and nopinone surfaces by combining environmental molecular beam (EMB) experiments and molecular dynamics (MD) simulations. The EMB method enables detailed studies of the dynamics and kinetics of water interacting with solid nopinone at 170−240 K and graphite coated with a molecularly thin nopinone layer at 200−270 K. MD simulations that mimic the experimental conditions have been performed to add insights into the molecular-level processes. Water molecules impinging on nopinone surfaces are efficiently trapped (≥97%), and only a minor fraction scatters inelastically while maintaining 35−65% of their incident kinetic energy (23.2 ± 1.0 kJ mol −1 ). A large fraction (60−80%) of the trapped molecules desorbs rapidly, whereas a small fraction (20−40%) remains on the surface for more than 10 ms. The MD calculations confirm both rapid water desorption and the occurrence of strongly bound surface states. A comparison of the experimental and computational results suggests that the formation of surface-bound water clusters enhances water uptake on the investigated surfaces.

Water and organic molecules are omnipresent in the environment, and their interactions are of central importance in many Earth system processes. Here we investigate molecular-level interactions between water and a nopinone surface using an environmental molecular beam (EMB) technique. Nopinone is a major reaction product formed during oxidation of β-pinene, a prominent compound emitted by coniferous trees, which has been found in both the gas and particle phases of atmospheric aerosol. The EMB method enables detailed studies of the dynamics and kinetics of DO molecules interacting with a solid nopinone surface at 202 K. Hyperthermal collisions between water and nopinone result in efficient trapping of water molecules, with a small fraction that scatter inelastically after losing 60-80% of their incident kinetic energy. While the majority of the trapped molecules rapidly desorb with a time constant τ less than 10 μs, a substantial fraction (0.32 ± 0.09) form strong bonds with the nopinone surface and remain in the condensed phase for milliseconds or longer. The interactions between water and nopinone are compared to results for recently studied water-alcohol and water-acetic acid systems, which display similar collision dynamics but differ with respect to the kinetics of accommodated water. The results contribute to an emerging surface science-based view and molecular-level description of organic aerosols in the atmosphere.

Molecular beam techniques are commonly used to obtain detailed information about reaction dynamics and kinetics of gas-surface interactions. These experiments are traditionally performed in vacuum and the dynamic state of surfaces under ambient conditions is thereby excluded from detailed studies. Herein we describe the development and demonstration of a new vacuum-gas interface that increases the accessible pressure range in environmental molecular beam (EMB) experiments. The interface consists of a grating close to a macroscopically flat surface, which allows for experiments at pressures above 1 Pa including angularly resolved measurements of the emitted flux. The technique is successfully demonstrated using key molecular beam experiments including elastic helium and inelastic water scattering from graphite, helium and light scattering from condensed adlayers, and water interactions with a liquid 1-butanol surface. The method is concluded to extend the pressure range and flexibility in EMB studies with implications for investigations of high pressure interface phenomena in diverse fields including catalysis, nanotechnology, environmental science, and life science. Potential further improvements of the technique are discussed.