Reaction Mechanism for Direct Proton Transfer from Carbonic Acid to a Strong Base in Aqueous Solution I: Acid and Base Coordinate and Charge Dynamics
Open accessAbstract
Protonation by carbonic acid H2CO3 of the strong base methylamine CH3NH2 in a neutral contact pair in aqueous solution is followed via Car-Parrinello molecular dynamics simulations. Proton transfer (PT) occurs to form an aqueous solvent-stabilized contact ion pair within 100 fs, a fast time scale associated with the compression of the acid-base hydrogen-bond (H-bond), a key reaction coordinate. This rapid barrierless PT is consistent with the carbonic acid-protonated base pKa difference that considerably favors the PT, and supports the view of intact carbonic acid as potentially important proton donor in assorted biological and environmental contexts. The charge redistribution within the H-bonded complex during PT supports a Mulliken picture of charge transfer from the nitrogen base to carbonic acid without altering the transferring hydrogen's charge from approximately midway between that of a hydrogen atom and that of a proton.
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Dissolution of CO2 from the atmosphere increases carbonate concentration in water.
“The dissolution of CO2 from the atmosphere also increases the carbonate concentration in the water matrix [37].”
From Advanced Oxidation Processes for Degradation of Water Pollutants—Ambivalent Impact of Carbonate Species: A Review (2023) · cites this paper as [37]
The Introduction (page unavailable) discusses aqueous CO2, carbonic acid and bicarbonate, but does not say that atmospheric CO2 dissolution increases carbonate concentration. Searches for atmospheric CO2 dissolution and carbonate concentration found no passage addressing that relationship. (LLM, conf=0.73)
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Rayaroth, M. P., Boczkaj, G., Aubry, O., Aravind, U. K., & Aravindakumar, C. T. (2023) · Water · doi:10.3390/w15081615 · Cited by 171 · see citing works
“The dissolution of CO 2 from the atmosphere also increases the carbonate concentration in the water matrix [37].”
- Authors
- Daschakraborty, S., Kiefer, P. M., Miller, Y., Motro, Y., Pines, D., Pines, E., & Hynes, J. T.
- Affiliations
- University of Colorado Boulder (US)
- Ben-Gurion University of the Negev (IL)
- Centre National de la Recherche Scientifique (FR)
- Corresponding author
- Daschakraborty, Snehasis
- Kiefer, Philip M.
- Pines, Ehud
- Hynes, James T.
- ORCID
- Venue
- The Journal of Physical Chemistry B
- Publisher
- American Chemical Society (ACS)
- Published
- 2016-03-02
- Volume
- 120
- Issue
- 9
- Pages
- 2271-2280
- ISSN
- 1520-5207 (ISSN-L)
- 1520-6106
- PMC
- PMC5763008
- OpenAlex
- W2280605182
- Cited by
- 30
- References
- 71
- Citations by year
- 2026: 4 · 2025: 2 · 2023: 2 · 2022: 1 · 2021: 1 · 2020: 2 · 2019: 5 · 2018: 6 · 2017: 5 · 2016: 2
- FWCI
- 2.75
- Type
- journal article
- Language
- en
- Open access
- green
- www.ncbi.nlm.nih.gov
- Locations
- The Journal of Physical Chemistry B (publishedVersion)
- PubMed (publishedVersion)
- Europe PMC (PubMed Central) (acceptedVersion)
- PubMed Central (acceptedVersion)
- Funders
- National Institutes of Health (PO 1000125420)
- Topics
- Physical Sciences › Chemistry › Organic Chemistry › Chemical Reaction Mechanisms
- Physical Sciences › Physics and Astronomy › Atomic and Molecular Physics, and Optics › Spectroscopy and Quantum Chemical Studies
- Physical Sciences › Chemistry › Physical and Theoretical Chemistry › Photochemistry and Electron Transfer Studies
- Keywords
- carbonic acid, proton transfer, methylamine, contact ion pairs, hydrogen bonding, reaction mechanism, charge redistribution, Mulliken population analysis, pKa difference, aqueous solutions, proton donors
- MeSH terms
- Carbonic Acid, Protons, Solutions, Water, Molecular Dynamics Simulation
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