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MP4 Study of the Anharmonic Coupling of the Shared Proton Stretching Vibration of the Protonated Water Dimer in Equilibrium and Transition States
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Number of Authors: 9
2017 (English)In: Journal of Physical Chemistry A, ISSN 1089-5639, E-ISSN 1520-5215, Vol. 121, no 10, 2151-2165 p.Article in journal (Refereed) Published
Abstract [en]

The structure and harmonic and anharmonic IR spectra of the protonated water dimer (PWD) were calculated in C-1,C- C-2.., and C-s, symmetry at the MP4/acc-pVTZ level of theory. We found that structure and IR spectra are practically identical in C-2 and C-1 symmetry, demonstrating that an equilibrium C-1 configuration of the PWD is not realized. Anharmonic coupling of the shared proton stretching-vibration with all other modes in the PWD in C-2 and C-s symmetry was the focus of this investigation. For this purpose, 28 two-dimensional potential energy surfaces (2D PES) were built at the MP4/acc-pVTZ level of theory and the corresponding vibrational Schrodinger equations were solved using the DVR method. Differences in the coupling of the investigated mode with other modes in the C-2 and C-s configurations, along with some factors that determine the red-or blue-shift of the stretching vibration frequency, were analyzed. We obtained a rather reasonable value of the stretching frequency of the bridging proton (1058.4 cm(-1)) unperturbed by Fermi resonance. The Fermi resonance between the fundamental vibration v7 and the combined vibration v(2) + v(6) of the same symmetry was analyzed through anharmonic second order perturbation theory calculations, as well as by 3D PES constructed using Q(2), Q(6), and Q(7) as normal coordinates. A significant (up to 50%) transfer of intensity from the fundamental vibration to the combined one was found. We have estimated the frequency of the bridging proton stretching vibration in the C-s configuration of the PWD based on calculations of the intrinsic anharmonicity and anharmonic double modes interactions at the MP4/acc-pVTZ level of theory (1261 cm(-1)).

Place, publisher, year, edition, pages
2017. Vol. 121, no 10, 2151-2165 p.
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Physical Sciences Chemical Sciences
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URN: urn:nbn:se:su:diva-142659DOI: 10.1021/acs.jpca.7b00536ISI: 000396969400010PubMedID: 28187260OAI: oai:DiVA.org:su-142659DiVA: diva2:1094941
Available from: 2017-05-11 Created: 2017-05-11 Last updated: 2017-05-11Bibliographically approved

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Pettersson, Lars G. M.
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