Uptake of N2O5 by aqueous aerosol unveiled using chemically accurate many-body potentials

Vinícius Wilian D Cruzeiro; Mirza Galib; David T Limmer; Andreas W Götz

doi:10.1038/s41467-022-28697-8

Uptake of N₂O₅ by aqueous aerosol unveiled using chemically accurate many-body potentials

Nat Commun. 2022 Mar 10;13(1):1266. doi: 10.1038/s41467-022-28697-8.

Authors

Vinícius Wilian D Cruzeiro^{1

2}, Mirza Galib³, David T Limmer^{4

5

6

7}, Andreas W Götz⁸

Affiliations

¹ San Diego Supercomputer Center, University of California San Diego, La Jolla, CA, 92093, USA.
² Department of Chemistry and Biochemistry, University of California San Diego, La Jolla, CA, 92093, USA.
³ Department of Chemistry, University of California, Berkeley, CA, USA.
⁴ Department of Chemistry, University of California, Berkeley, CA, USA. dlimmer@berkeley.edu.
⁵ Kavli Energy NanoScience Institute, Berkeley, CA, USA. dlimmer@berkeley.edu.
⁶ Materials Science Division, Lawrence Berkeley National Laboratory, Berkeley, CA, USA. dlimmer@berkeley.edu.
⁷ Chemical Science Division, Lawrence Berkeley National Laboratory, Berkeley, CA, USA. dlimmer@berkeley.edu.
⁸ San Diego Supercomputer Center, University of California San Diego, La Jolla, CA, 92093, USA. agoetz@sdsc.edu.

Abstract

The 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.