The Determination of Free Energy of Hydration of Water Ions from First Principles.

Autor: Butin O; InterX, Inc. (a subsidiary of NeoTX Therapeutics, Ltd.), 805 Allston Way, Berkeley, California 94710, United States., Pereyaslavets L; InterX, Inc. (a subsidiary of NeoTX Therapeutics, Ltd.), 805 Allston Way, Berkeley, California 94710, United States., Kamath G; InterX, Inc. (a subsidiary of NeoTX Therapeutics, Ltd.), 805 Allston Way, Berkeley, California 94710, United States., Illarionov A; InterX, Inc. (a subsidiary of NeoTX Therapeutics, Ltd.), 805 Allston Way, Berkeley, California 94710, United States., Sakipov S; InterX, Inc. (a subsidiary of NeoTX Therapeutics, Ltd.), 805 Allston Way, Berkeley, California 94710, United States., Kurnikov IV; InterX, Inc. (a subsidiary of NeoTX Therapeutics, Ltd.), 805 Allston Way, Berkeley, California 94710, United States., Voronina E; InterX, Inc. (a subsidiary of NeoTX Therapeutics, Ltd.), 805 Allston Way, Berkeley, California 94710, United States.; Skobeltsyn Institute of Nuclear Physics, Lomonosov Moscow State University, Moscow 119991, Russia., Ivahnenko I; InterX, Inc. (a subsidiary of NeoTX Therapeutics, Ltd.), 805 Allston Way, Berkeley, California 94710, United States., Leontyev I; InterX, Inc. (a subsidiary of NeoTX Therapeutics, Ltd.), 805 Allston Way, Berkeley, California 94710, United States., Nawrocki G; InterX, Inc. (a subsidiary of NeoTX Therapeutics, Ltd.), 805 Allston Way, Berkeley, California 94710, United States., Darkhovskiy M; InterX, Inc. (a subsidiary of NeoTX Therapeutics, Ltd.), 805 Allston Way, Berkeley, California 94710, United States., Olevanov M; InterX, Inc. (a subsidiary of NeoTX Therapeutics, Ltd.), 805 Allston Way, Berkeley, California 94710, United States.; Department of Physics, Lomonosov Moscow State University, Moscow 119991, Russia., Cherniavskyi YK; InterX, Inc. (a subsidiary of NeoTX Therapeutics, Ltd.), 805 Allston Way, Berkeley, California 94710, United States., Lock C; InterX, Inc. (a subsidiary of NeoTX Therapeutics, Ltd.), 805 Allston Way, Berkeley, California 94710, United States.; Department of Neurology and Neurological Sciences, Stanford University School of Medicine, Palo Alto, California 94304, United States., Greenslade S; InterX, Inc. (a subsidiary of NeoTX Therapeutics, Ltd.), 805 Allston Way, Berkeley, California 94710, United States., Kornberg RD; Department of Structural Biology, Stanford University School of Medicine, Stanford, California 94305, United States., Levitt M; Department of Structural Biology, Stanford University School of Medicine, Stanford, California 94305, United States., Fain B; InterX, Inc. (a subsidiary of NeoTX Therapeutics, Ltd.), 805 Allston Way, Berkeley, California 94710, United States.
Jazyk: angličtina
Zdroj: Journal of chemical theory and computation [J Chem Theory Comput] 2024 Jun 25; Vol. 20 (12), pp. 5215-5224. Date of Electronic Publication: 2024 Jun 06.
DOI: 10.1021/acs.jctc.3c01411
Abstrakt: We model the autoionization of water by determining the free energy of hydration of the major intermediate species of water ions. We represent the smallest ions─the hydroxide ion OH - , the hydronium ion H 3 O + , and the Zundel ion H 5 O 2 + ─by bonded models and the more extended ionic structures by strong nonbonded interactions (e.g., the Eigen H 9 O 4 + = H 3 O + + 3(H 2 O) and the Stoyanov H 13 O 6 + = H 5 O 2 + + 4(H 2 O)). Our models are faithful to the precise QM energies and their components to within 1% or less. Using the calculated free energies and atomization energies, we compute the p K a of pure water from first principles as a consistency check and arrive at a value within 1.3 log units of the experimental one. From these calculations, we conclude that the hydronium ion, and its hydrated state, the Eigen cation, are the dominant species in the water autoionization process.
Databáze: MEDLINE
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