Features in Vibrational Spectra Induced by Ar-Tagging for H3O(+)Arm, m = 0-3

Understanding the spectral features for solvated hydronium has been hindered due to the strong and complex vibrational couplings that lead to broad bands in the aqueous phase. In this work, utilizing ab initio vibrational calculations, we determine how the vibrational couplings induced by the Ar mic...

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Bibliographic Details
Published in:The journal of physical chemistry. A, Molecules, spectroscopy, kinetics, environment, & general theory Molecules, spectroscopy, kinetics, environment, & general theory, 2015-11, Vol.119 (44), p.10887-10892
Main Authors: Li, Jheng-Wei, Morita, Masato, Takahashi, Kaito, Kuo, Jer-Lai
Format: Article
Language:English
Subjects:
Argon - chemistry
Computer Simulation
Spectrum Analysis - methods
Vibration
Water - chemistry
Online Access:Get full text
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Summary:Understanding the spectral features for solvated hydronium has been hindered due to the strong and complex vibrational couplings that lead to broad bands in the aqueous phase. In this work, utilizing ab initio vibrational calculations, we determine how the vibrational couplings induced by the Ar microsolvation in H3O(+)Arm m = 0-3 affect the observed spectra. With theoretical peak intensities and peak positions, we assign the experimental spectra. We also show that an increase in the number of Ar atoms results in an anticooperative blue shifting in the Ar-tagged OH stretching bands. This change in peak position of the OH stretching fundamental modulates the Fermi resonance with the bending overtone. This is observed as a distinct doublet feature at 3200 cm(-1) with varying intensities for H3O(+)Ar2 and H3O(+)Ar3. The coupling between the in-plane rotation of the hydronium and the bending modes of H3O(+) leads to the existence of a strong association bands around 1900 cm(-1).
ISSN:1520-5215
DOI:10.1021/acs.jpca.5b08898