Molecular Simulations of Halomethanes at the Air/Ice Interface

Abstract

Halogenated organics are emitted into the atmosphere from a variety of sources of both natural and anthropogenic origin. Their uptake at the surface of aerosols can affect their reactivity, for example, in processes that take part in ozone destruction due to production of reactive chlorine, bromine, and iodine radicals. Classical molecular dynamics (MD) simulations are carried out to investigate the interaction of small halomethane molecules of atmospheric relevance with a crystalline ice surface. The following halomethanes were studied: CH3Cl, CH2Cl2, CHCl3, CH3Br, CH2Br2, and CHBr3. MD simulations provide an invaluable insight into the adsorption behavior of halomethanes species. The adsorption energy is increasing as the number of halogen atoms is increasing. Moreover, brominated methanes exhibit a stronger interaction with the ice than their chlorinated analogs. Implications for the atmospheric chemistry are discussed.