Uptake of N2O5 by aqueous aerosol unveiled using chemically accurate many-body potentials
Abstract
The reactive uptake of N2O5to 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 N2O5in water. The free energy profile highlights that N2O5is 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 N2O5in more complex solutions.
Document Details
- Document Type
- Pub Defense Publication
- Publication Date
- Mar 10, 2022
- Source ID
- 10.1038/s41467-022-28697-8
Entities
People
- Andreas W Götz
- David T Limmer
- Mirza Galib
- Vinícius Wilian D. Cruzeiro