Disentangling Acid-Base Chemistry through Blue Shifting Hydrogen Bond Contributions.

Autor: Kelly JT; Environmental and Legacy Management, Savannah River National Laboratory, 301 Gateway Drive, Aiken, SC-29803, USA., McNamara LE; Global Security Directorate, Savannah River National Laboratory, 301 Gateway Drive, Aiken, SC-29803, USA., Gilbraith WE; Environmental and Legacy Management, Savannah River National Laboratory, 301 Gateway Drive, Aiken, SC-29803, USA., Goetzman CM; Environmental and Legacy Management, Savannah River National Laboratory, 301 Gateway Drive, Aiken, SC-29803, USA., Hoover ME; Global Security Directorate, Savannah River National Laboratory, 301 Gateway Drive, Aiken, SC-29803, USA., Lascola RJ; Environmental and Legacy Management, Savannah River National Laboratory, 301 Gateway Drive, Aiken, SC-29803, USA.
Jazyk: angličtina
Zdroj: Chemphyschem : a European journal of chemical physics and physical chemistry [Chemphyschem] 2024 Oct 16; Vol. 25 (20), pp. e202400029. Date of Electronic Publication: 2024 Aug 23.
DOI: 10.1002/cphc.202400029
Abstrakt: The blue shifting of vibrational frequencies in hydrogen bonded molecules, as observed in aqueous environments, has been attributed to local partial charge transfer from solvation. Here, we extrapolate the blue shift model to the stronger ionic interactions between hydrogen bond acceptors associated with protonation through augmented pH levels and competitive interactions with counter ion pairing. The chemical model we utilize in this work is the aqueous pyridine-pyridinium equilibrium to characterize the blue shifts observed in the pyridinium chloride ionic system. The observed agreement between observed experimental and calculated spectral shifts shows that the blue shifting model can be extrapolated to stronger interactions and accurately describe the nature of the hydrogen bond.
(© 2024 Wiley-VCH GmbH.)
Databáze: MEDLINE
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