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Issue 8, 2014
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On the protonation of water

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Abstract

Imaging photoelectron photoion coincidence (iPEPICO) spectroscopy on isolated water molecules and water dimers establishes a new route to determining the water proton affinity (PA) with unprecedented accuracy. A floating thermochemical cycle constructed from the OH+ and H3O+ appearance energies and three other spectroscopic values establishes the water PA as 683.22 ± 0.25 kJ mol−1 at 0 K, which converts to 688.81 ± 0.25 kJ mol−1 at room temperature. The experimental results are corroborated by a hierarchy of coupled-cluster calculations up to pentuple excitations and septuple-ζ basis set. Combined with diagonal Born–Oppenheimer and Dirac–Coulomb–Gaunt relativistic corrections, they provide the best theoretical estimate for both the hydronium ion's geometry and a water PA of 683.5 ± 0.4 kJ mol−1 and 689.1 ± 0.4 kJ mol−1 at 0 K and 298.15 K, respectively.

Graphical abstract: On the protonation of water

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Article information


Submitted
16 Mar 2014
Accepted
12 May 2014
First published
12 May 2014

This article is Open Access
All publication charges for this article have been paid for by the Royal Society of Chemistry

Chem. Sci., 2014,5, 3057-3063
Article type
Edge Article
Author version available

On the protonation of water

A. Bodi, J. Csontos, M. Kállay, S. Borkar and B. Sztáray, Chem. Sci., 2014, 5, 3057
DOI: 10.1039/C4SC00791C

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