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    Water-anion hydrogen bonding dynamics: Ultrafast IR experiments and simulations

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    ThompsonW_2017.pdf (4.976Mb)
    Issue Date
    2017-06-15
    Author
    Yamada, Steven A.
    Thompson, Ward H.
    Fayer, Michael D.
    Publisher
    AIP Publishing
    Type
    Article
    Article Version
    Scholarly/refereed, publisher version
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    Abstract
    Many of water’s remarkable properties arise from its tendency to form an intricate and robust hydrogen bond network. Understanding the dynamics that govern this network is fundamental to elucidating the behavior of pure water and water in biological and physical systems. In ultrafast nonlinear infrared experiments, the accessible time scales are limited by water’s rapid vibrational relaxation (1.8 ps for dilute HOD in H2O), precluding interrogation of slow hydrogen bond evolution in non-bulk systems. Here, hydrogen bonding dynamics in bulk D2O were studied from the perspective of the much longer lived (36.2 ps) CN stretch mode of selenocyanate (SeCN−) using polarization selective pump-probe (PSPP) experiments, two-dimensional infrared (2D IR) vibrational echo spectroscopy, and molecular dynamics simulations. The simulations make use of the empirical frequency mapping approach, applied to SeCN− for the first time. The PSPP experiments and simulations show that the orientational correlation function decays via fast (2.0 ps) restricted angular diffusion (wobbling-in-a-cone) and complete orientational diffusive randomization (4.5 ps). Spectral diffusion, quantified in terms of the frequency-frequency correlation function, occurs on two time scales. The initial 0.6 ps time scale is attributed to small length and angle fluctuations of the hydrogen bonds between water and SeCN−. The second 1.4 ps measured time scale, identical to that for HOD in bulk D2O, reports on the collective reorganization of the water hydrogen bond network around the anion. The experiments and simulations provide details of the anion-water hydrogen bonding and demonstrate that SeCN− is a reliable vibrational probe of the ultrafast spectroscopy of water.
    Description
    The following article appeared in Yamada, S. A., Thompson, W. H., & Fayer, M. D. (2017). Water-anion hydrogen bonding dynamics: Ultrafast IR experiments and simulations. The Journal of Chemical Physics, 146(23), 234501.) and may be found at https://aip.scitation.org/doi/10.1063/1.4984766.
    URI
    http://hdl.handle.net/1808/27375
    DOI
    https://doi.org/10.1063/1.4984766
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    • Chemistry Scholarly Works [553]
    Citation
    Yamada, S. A., Thompson, W. H., & Fayer, M. D. (2017). Water-anion hydrogen bonding dynamics: Ultrafast IR experiments and simulations. The Journal of Chemical Physics, 146(23), 234501.

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    785-864-8983

    KU Libraries
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    Contact KU ScholarWorks
    785-864-8983
    KU Libraries
    1425 Jayhawk Blvd
    Lawrence, KS 66045
    785-864-8983

    KU Libraries
    1425 Jayhawk Blvd
    Lawrence, KS 66045
    Image Credits
     

     

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