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Infrared Spectra of Protonated Water Clusters, H+(H2O)4, in Eigen and Zundel Forms Studied by Vibrational Quasi-Degenerate Perturbation Theory

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    Infrared Spectra of Protonated Water Clusters, H+(H2O)4, in Eigen and Zundel Forms Studied by Vibrational Quasi-Degenerate Perturbation Theory
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    † †Theoretical Molecular Science Laboratory and ‡iTHES, RIKEN, 2-1 Hirosawa, Wako, Saitama 351-0198, Japan
    *(K.Y.) E-mail: [email protected]
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    The Journal of Physical Chemistry A

    Cite this: J. Phys. Chem. A 2017, 121, 12, 2386–2398
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    https://doi.org/10.1021/acs.jpca.6b11189
    Published March 9, 2017
    Copyright © 2017 American Chemical Society
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    Abstract

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    The infrared spectrum of H+(H2O)4 recently observed in a wide spectral range has shown a series of bands in a range of 1700–2500 cm–1, which can not be understood by the standard harmonic normal mode analysis. Here, we theoretically investigate the origin of these bands with a focus on (1) the possibility of coexistence of multiple isomers in the Eigen [H3O+(H2O)3] and Zundel [H5O2+(H2O)2] forms and (2) the effect of anharmonic coupling that gives rise to nonzero intensities for overtones and combination bands. Anharmonic vibrational calculations are carried out for the Eigen and Zundel clusters by the second-order vibrational quasi-degenerate perturbation theory (VQDPT2) based on optimized coordinates. The anharmonic potential energy surface and the dipole moment surfaces are generated by a multiresolution approach combining one-dimensional (1D) grid potential functions derived from CCSD(T)-F12, 2D and 3D grid potential functions derived from B3LYP for important coupling terms, and a quartic force field derived from B3LYP for less important terms. The spectrum calculated for the Eigen cluster is in excellent agreement with the experiment, assigning the bands in the range of 1700–2500 cm–1 to overtones and combination bands of a H3O+ moiety in line with recent reports [ J. Phys. Chem. A 2015, 119, 9425; Science 2016, 354, 1131]. On the other hand, characteristic OH stretching bands of the Zundel cluster is found to be absent in the experimental spectrum. We therefore conclude that the experimental spectrum originates solely from the Eigen cluster. Nonetheless, the present calculation for the Eigen cluster poorly reproduces a band observed at 1765 cm–1. A possible nature of this band is discussed.

    Copyright © 2017 American Chemical Society

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    The Supporting Information is available free of charge on the ACS Publications website at DOI: 10.1021/acs.jpca.6b11189.

    • Cartesian coordinates (Table S1) and harmonic frequencies (Table S2) of the Eigen and Zundel clusters obtained by B3LYP/aug-cc-pVTZ, CCSD(T)-F12/aug-cc-pVDZ, and the multiresolution PES. normal coordinates not considered in this work (Figure S1); plots of the IR spectrum of the Eigen cluster using fwhm of 5, 10, and 20 cm–1 for the Lorentz functions to construct the spectrum (Figure S2); computational details on oc-VSCF calculations; the number of important coupling terms in normal and optimized coordinates (Table S3); comparison of normal and optimized coordinates, with normal and optimized coordinates (Figure S3 and S4) and harmonic frequency (Table S4) of the Eigen cluster; weight of H3O+ and water molecules (Table S5); normal and optimized coordinates (Figure S5 and S6) and harmonic frequency (Table S6) of the Zundel cluster; weight of H5O2+ and water molecules (Table S7); vibrational wave function analysis: 9D/3D × 3, 18D, and 24D (Tables S8, S9, and S10) for the Eigen cluster, and 12D/3D × 2, 16D/3D × 2, and 26D (Table S11, S12, and S13) for the Zundel cluster (PDF)

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    The Journal of Physical Chemistry A

    Cite this: J. Phys. Chem. A 2017, 121, 12, 2386–2398
    Click to copy citationCitation copied!
    https://doi.org/10.1021/acs.jpca.6b11189
    Published March 9, 2017
    Copyright © 2017 American Chemical Society
    Request reuse permissions

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