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Annual Review of Physical Chemistry

Volume 72, 2021

Demystifying the Diffuse Vibrational Spectrum of Aqueous Protons Through Cold Cluster Spectroscopy

Abstract

The ease with which the pH is routinely determined for aqueous solutions masks the fact that the cationic product of Arrhenius acid dissolution, the hydrated proton, or H+(aq), is a remarkably complex species. Here, we review how results obtained over the past 30 years in the study of H+⋅(HO) cluster ions isolated in the gas phase shed light on the chemical nature of H+(aq). This effort has also revealed molecular-level aspects of the Grotthuss relay mechanism for positive-charge translocation in water. Recently developed methods involving cryogenic cooling in radiofrequency ion traps and the application of two-color, infrared–infrared (IR–IR) double-resonance spectroscopy have established a clear picture of how local hydrogen-bond topology drives the diverse spectral signatures of the excess proton. This information now enables a new generation of cluster studies designed to unravel the microscopic mechanics underlying the ultrafast relaxation dynamics displayed by H+(aq).

Keyword(s): cluster chemistry, cryogenic vibrational predissociation spectroscopy, ions, protons, solvation
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/content/journals/10.1146/annurev-physchem-061020-053456
2021-04-20
2024-04-20
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/content/journals/10.1146/annurev-physchem-061020-053456
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Demystifying the Diffuse Vibrational Spectrum of Aqueous Protons Through Cold Cluster Spectroscopy
Annual Review of Physical Chemistry 72, 667 (2021); https://doi.org/10.1146/annurev-physchem-061020-053456
/content/journals/10.1146/annurev-physchem-061020-053456
/content/journals/10.1146/annurev-physchem-061020-053456
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