Issue 10, 2013

Molecular simulations of green leaf volatiles and atmospheric oxidants on air/water interfaces

Abstract

Green leaf volatiles (GLVs) are oxygenated hydrocarbons that are emitted by plants, especially under stress conditions such as mechanical damage and local weather changes. GLVs can react with photochemically-generated oxidants (e.g., OH radicals) in atmospheric water drops, and contribute to the formation of secondary organic aerosols (SOAs). Here we investigated the adsorption of a gas phase GLV, 2-methyl-3-buten-2-ol (MBO) and OH radicals on atmospheric air/water interfaces using classical molecular dynamics (MD) simulations and potential of mean force (PMF) calculations. Our models can reproduce experimental values of the free energy of hydration of MBO and ˙OH, as well as 1-octanol/water partition coefficients of MBO determined experimentally in this study. Both MBO and ˙OH have a strong thermodynamic incentive to remain at the air/water interface, with their density profiles overlapping significantly at the interface. These results suggest that chemical reactions between MBO and ˙OH are more likely to take place at the interface, rather than inside the bulk of water droplets or in the vapor phase. We found a significant number of contacts between MBO and ˙OH in our simulations, which could lead to reactions between these two species.

Graphical abstract: Molecular simulations of green leaf volatiles and atmospheric oxidants on air/water interfaces

Article information

Article type
Paper
Submitted
17 Nov 2012
Accepted
11 Jan 2013
First published
04 Feb 2013

Phys. Chem. Chem. Phys., 2013,15, 3583-3592

Molecular simulations of green leaf volatiles and atmospheric oxidants on air/water interfaces

T. P. Liyana-Arachchi, C. Stevens, A. K. Hansel, F. S. Ehrenhauser, K. T. Valsaraj and F. R. Hung, Phys. Chem. Chem. Phys., 2013, 15, 3583 DOI: 10.1039/C3CP44090G

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