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dc.contributor.authorYamada, Steven A.
dc.contributor.authorThompson, Ward H.
dc.contributor.authorFayer, Michael D.
dc.identifier.citationYamada, 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.en_US
dc.descriptionThe 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
dc.description.abstractMany 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.en_US
dc.publisherAIP Publishingen_US
dc.titleWater-anion hydrogen bonding dynamics: Ultrafast IR experiments and simulationsen_US
kusw.kuauthorThompson, Ward H.
kusw.oanotesPer SHERPA/RoMEO 11/15/2018: Author's Pre-print: green tick author can archive pre-print (ie pre-refereeing) Author's Post-print: green tick author can archive post-print (ie final draft post-refereeing) Publisher's Version/PDF: grey tick subject to Restrictions below, author can archive publisher's version/PDF General Conditions:

Authors retain copyright Author's pre-print on arXiv or preprint server Author's post-print on free e-print servers or arXiv, author's personal website, institutional website, funding-agency repository, institutional repository, or social academic network upon acceptance Publishers version/PDF may be used on author's personal website, arXiv, institutional website, institutional repository, funders designated repository or private forums on social academic network after 12 months embargo Must link to publisher version or journal home page Publisher copyright and source must be acknowledged with set statement (see policy) NIH-funded articles are automatically deposited with PubMed Central with open access after 12
kusw.oaversionScholarly/refereed, publisher versionen_US
kusw.oapolicyThis item meets KU Open Access policy criteria.en_US

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