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

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 H 2O), precluding interrogation of slow hydrogen bond evolution in non-bulk systems. Here in this paper, hydrogen bonding dynamics in bulk D 2O 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 betweenmore » water and SeCN -. The second 1.4 ps measured time scale, identical to that for HOD in bulk D 2O, reports on the collective reorganization of the water hydrogen bond network around the anion. Lastly, 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.« less
Authors:
ORCiD logo [1] ; ORCiD logo [2] ; ORCiD logo [1]
  1. Stanford Univ., CA (United States). Dept. of Chemistry
  2. Univ. of Kansas, Lawrence, KS (United States). Dept. of Chemistry
Publication Date:
Grant/Contract Number:
FG03-84ER13251; FG02-05ER15708
Type:
Accepted Manuscript
Journal Name:
Journal of Chemical Physics
Additional Journal Information:
Journal Volume: 146; Journal Issue: 23; Journal ID: ISSN 0021-9606
Publisher:
American Institute of Physics (AIP)
Research Org:
Stanford Univ., CA (United States)
Sponsoring Org:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
OSTI Identifier:
1473890
Alternate Identifier(s):
OSTI ID: 1411099

Yamada, Steven A., Thompson, Ward H., and Fayer, Michael D.. Water-anion hydrogen bonding dynamics: Ultrafast IR experiments and simulations. United States: N. p., Web. doi:10.1063/1.4984766.
Yamada, Steven A., Thompson, Ward H., & Fayer, Michael D.. Water-anion hydrogen bonding dynamics: Ultrafast IR experiments and simulations. United States. doi:10.1063/1.4984766.
Yamada, Steven A., Thompson, Ward H., and Fayer, Michael D.. 2017. "Water-anion hydrogen bonding dynamics: Ultrafast IR experiments and simulations". United States. doi:10.1063/1.4984766. https://www.osti.gov/servlets/purl/1473890.
@article{osti_1473890,
title = {Water-anion hydrogen bonding dynamics: Ultrafast IR experiments and simulations},
author = {Yamada, Steven A. and Thompson, Ward H. and Fayer, Michael D.},
abstractNote = {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 in this paper, 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. Lastly, 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.},
doi = {10.1063/1.4984766},
journal = {Journal of Chemical Physics},
number = 23,
volume = 146,
place = {United States},
year = {2017},
month = {6}
}

Works referenced in this record:

Universal Solvation Model Based on Solute Electron Density and on a Continuum Model of the Solvent Defined by the Bulk Dielectric Constant and Atomic Surface Tensions
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