Hydroxymethanesulfonate formation accelerated at the air-water interface by synergistic enthalpy-entropy effects

Jifan Li, Weiqiang Tang, Jiabao Zhu, Jinrong Yang () and Xiao He ()
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Jifan Li: East China Normal University
Weiqiang Tang: East China University of Science and Technology
Jiabao Zhu: East China Normal University
Jinrong Yang: East China Normal University
Xiao He: East China Normal University

Nature Communications, 2025, vol. 16, issue 1, 1-17

Abstract: Abstract Hydroxymethanesulfonate is a key organosulfate linked to severe fine-particle pollution in fog and clouds, yet its rapid formation mechanism at the air-water interface remains elusive. Here, using metadynamics-biased ab initio molecular dynamics simulations, high-level quantum chemical calculations and reaction density functional theory, we reveal that synergistic enthalpy-entropy effects govern the nucleophilic addition between bisulfite and formaldehyde. Compared to the gaseous reaction, the aqueous reaction faces a ~5.0 kcal/mol water reorganization barrier, partly offset by polarization effects. Ab initio molecular dynamics simulations show hydrogen bonding networks facilitate proton transfer via the Grotthuss mechanism, reducing activation entropy by ~5.5 kcal/mol. At the interface, partial solvation and restricted formaldehyde motion lower the enthalpy and configurational entropy by ~1.0 and ~0.9 kcal/mol, respectively, alongside a 1.9 kcal/mol electric field effect. These combined effects enhance the interfacial reaction rate by two orders of magnitude, offering insights into heterogeneous chemistry and strategies for winter haze mitigation.

Date: 2025
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DOI: 10.1038/s41467-025-59712-3

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