title: Surface residence and uptake of methyl chloride and methyl alcohol at the air/water interface studied by vibrational sum frequency spectroscopy and molecular dynamics.
abstract: Vibrational sum frequency generation (VSFG) spectroscopy and molecular dynamics (MD) simulations are used to study the surface residence and organization of gas-phase methyl halide and methyl alcohol molecules adsorbed to the air/water interface, while Raman spectroscopy is used to detect the uptake of the gas-phase species into the bulk aqueous phase. Spectroscopy results reveal the presence of methyl alcohol in the bulk and at the surface. Methyl chloride is detected in the bulk, but not at the surface. This indicates that methyl alcohol adsorbs to the aqueous surface in a layer that is ordered, in agreement with previous studies, and is also readily taken up into the bulk aqueous phase, whereas methyl chloride adsorbs, but, while being taken up into the bulk liquid, has lower surface number density and/or forms a more disordered surface layer than methyl alcohol. MD simulations show that methyl halide molecules transition readily between the gas phase and interface, resulting in significantly shorter residence times at the surface for the methyl halides relative to methyl alcohol. Both the geometries that the methyl species adopt at the interface and the interactions between the methyl species and the interfacial water molecules differ for the halides and the alcohol. Complementary studies of butyl species show similar results: butyl alcohol adsorbs to the aqueous surface in a layer that exhibits a certain degree of order corresponding to the chains aligned along the surface normal, while a markedly more disordered surface layer and shorter residence times are observed in MD simulations for the butyl halides as compared to the alcohol. Desorption from the interface was found to be less frequent for the butyl halides than for the methyl halides by MD simulations. Although Raman studies show uptake of the butyl alcohol into the bulk phase, neither Raman studies nor MD simulations provide any evidence for uptake of the butyl halides into the bulk phase. The profound difference in preferred orientations between alkyl halides and alcohols at the aqueous surface, with the halogen atom of the alkyl halides being to a large degree exposed to the vapor phase, is likely to have consequences for chemistry of alkyl halides adsorbed on the surface of atmospheric aerosol particles.
authors.affiliation: Department of Chemistry, The Ohio State University, 100 West 18th Avenue, Columbus, Ohio 43210, USA.
authors.forename: Kandice
authors.initials: K
authors.lastname: Harper
authors.forename: Babak
authors.initials: B
authors.lastname: Minofar
authors.forename: M Roxana
authors.initials: MR
authors.lastname: Sierra-Hernandez
authors.forename: Nadia N
authors.initials: NN
authors.lastname: Casillas-Ituarte
authors.forename: Martina
authors.initials: M
authors.lastname: Roeselova
authors.forename: Heather C
authors.initials: HC
authors.lastname: Allen
mesh_terms: D000327:Adsorption; D000388:Air / Q000032:analysis*; D000432:Methanol / Q000032:analysis* / Q000737:chemistry; D008737:Methyl Chloride / Q000032:analysis* / Q000737:chemistry; D008956:Models, Chemical; D013059:Spectrum Analysis, Raman; D013499:Surface Properties; D014732:Vibration; D014867:Water / Q000032:analysis*
chemical_list: D014867:Water; D008737:Methyl Chloride; D000432:Methanol