Abstract
AbstractThe reactive uptake of N2O5 to aqueous aerosol is a major loss channel for nitrogen oxides in the troposphere. Despite its importance, a quantitative picture of the uptake mechanism is missing. Here we use molecular dynamics simulations with a data-driven many-body model of coupled-cluster accuracy to quantify thermodynamics and kinetics of solvation and adsorption of N2O5 in water. The free energy profile highlights that N2O5 is selectively adsorbed to the liquid–vapor interface and weakly solvated. Accommodation into bulk water occurs slowly, competing with evaporation upon adsorption from gas phase. Leveraging the quantitative accuracy of the model, we parameterize and solve a reaction–diffusion equation to determine hydrolysis rates consistent with experimental observations. We find a short reaction–diffusion length, indicating that the uptake is dominated by interfacial features. The parameters deduced here, including solubility, accommodation coefficient, and hydrolysis rate, afford a foundation for which to consider the reactive loss of N2O5 in more complex solutions.
Publisher
Springer Science and Business Media LLC
Subject
General Physics and Astronomy,General Biochemistry, Genetics and Molecular Biology,General Chemistry,Multidisciplinary
Reference71 articles.
1. Peter, T. Microphysics and heterogeneous chemistry of polar stratospheric clouds. Annu. Rev. Phys. Chem. 48, 785–822 (1997).
2. Finlayson-Pitts, B. J. & Pitts Jr, J. N. Chemistry of the Upper and Lower Atmosphere: Theory, Experiments, and Applications (Elsevier, 2000).
3. Ravishankara, A. Heterogeneous and multiphase chemistry in the troposphere. Science 276, 1058–1065 (1997).
4. Pöschl, U. & Shiraiwa, M. Multiphase chemistry at the atmosphere–biosphere interface influencing climate and public health in the anthropocene. Chem. Rev. 115, 4440–4475 (2015).
5. Holmes, C. D. et al. The role of clouds in the tropospheric NOx cycle: A new modeling approach for cloud chemistry and its global implications. Geophys. Res. Lett. 46, 4980–4990 (2019).
Cited by
6 articles.
订阅此论文施引文献
订阅此论文施引文献，注册后可以免费订阅5篇论文的施引文献，订阅后可以查看论文全部施引文献