The Reactivity-Enhancing Role of Water Clusters in Ammonia Aqueous Solutions

0583648 - BFÚ 2024 RIV US eng J - Journal Article
Cassone, G. - Saija, F. - Šponer, Jiří - Shaik, S.
The Reactivity-Enhancing Role of Water Clusters in Ammonia Aqueous Solutions.
Journal of Physical Chemistry Letters. Roč. 14, č. 35 (2023), s. 7808-7813. ISSN 1948-7185
Institutional support: RVO:68081707
Keywords : electric-fields * catalysis
OECD category: Atomic, molecular and chemical physics (physics of atoms and molecules including collision, interaction with radiation, magnetic resonances, Mössbauer effect)
Impact factor: 5.7, year: 2022
Method of publishing: Open access
https://pubs.acs.org/doi/10.1021/acs.jpclett.3c01810

Among the many prototypical acid-base systems, ammonia aqueous solutions hold a privileged place, owing to their omnipresence in various planets and their universal solvent character. Although the theoretical optimal water-ammonia molar ratio to form NH4+ and OH- ion pairs is 50:50, our ab initio molecular dynamics simulations show that the tendency of forming these ionic species is inversely (directly) proportional to the amount of ammonia (water) in ammonia aqueous solutions, up to a water-ammonia molar ratio of similar to 75:25. Here we prove that the reactivity of these liquid mixtures is rooted in peculiar microscopic patterns emerging at the H-bonding scale, where the highly orchestrated motion of 5 solvating molecules modulates proton transfer events through local electric fields. This study demonstrates that the reaction of water with NH3 is catalyzed by a small cluster of water molecules, in which an H atom possesses a high local electric field, much like the effect observed in catalysis by water droplets [PNAS2023, 120 ,e2301206120].
Permanent Link: https://hdl.handle.net/11104/0351670