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Title: Delocalization and stretch-bend mixing of the HOH bend in liquid water

Abstract

Liquid water’s rich sub-picosecond vibrational dynamics arise from the interplay of different high- and low-frequency modes evolving in a strong yet fluctuating hydrogen bond network. Recent studies of the OH stretching excitations of H 2O indicate that they are delocalized over several molecules, raising questions about whether the bending vibrations are similarly delocalized. In this paper, we take advantage of an improved 50 fs time-resolution and broadband infrared (IR) spectroscopy to interrogate the 2D IR lineshape and spectral dynamics of the HOH bending vibration of liquid H2O. Indications of strong bend-stretch coupling are observed in early time 2D IR spectra through a broad excited state absorption that extends from 1500 cm -1 to beyond 1900 cm -1, which corresponds to transitions from the bend to the bend overtone and OH stretching band between 3150 and 3550 cm -1. Pump-probe measurements reveal a fast 180 fs vibrational relaxation time, which results in a hot-ground state spectrum that is the same as observed for water IR excitation at any other frequency. The fastest dynamical time scale is 80 fs for the polarization anisotropy decay, providing evidence for the delocalized or excitonic character of the bend. Finally, normal mode analysis conducted on watermore » clusters extracted from molecular dynamics simulations corroborate significant stretch-bend mixing and indicate delocalization of δ HOH on 2-7 water molecules.« less

Authors:
ORCiD logo [1]; ORCiD logo [1]; ORCiD logo [2]; ORCiD logo [1]; ORCiD logo [1]
  1. Univ. of Chicago, IL (United States)
  2. Indian Inst. of Science, Bangalore (India)
Publication Date:
Research Org.:
Univ. of Chicago, IL (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22). Chemical Sciences, Geosciences & Biosciences Division; USDOE
OSTI Identifier:
1600623
Alternate Identifier(s):
OSTI ID: 1376763
Grant/Contract Number:  
SC0014305; FOA-0000995
Resource Type:
Accepted Manuscript
Journal Name:
Journal of Chemical Physics
Additional Journal Information:
Journal Volume: 147; Journal Issue: 8; Journal ID: ISSN 0021-9606
Publisher:
American Institute of Physics (AIP)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats

Carpenter, William B., Fournier, Joseph A., Biswas, Rajib, Voth, Gregory A., and Tokmakoff, Andrei. Delocalization and stretch-bend mixing of the HOH bend in liquid water. United States: N. p., 2017. Web. doi:10.1063/1.4987153.
Carpenter, William B., Fournier, Joseph A., Biswas, Rajib, Voth, Gregory A., & Tokmakoff, Andrei. Delocalization and stretch-bend mixing of the HOH bend in liquid water. United States. doi:10.1063/1.4987153.
Carpenter, William B., Fournier, Joseph A., Biswas, Rajib, Voth, Gregory A., and Tokmakoff, Andrei. Thu . "Delocalization and stretch-bend mixing of the HOH bend in liquid water". United States. doi:10.1063/1.4987153. https://www.osti.gov/servlets/purl/1600623.
@article{osti_1600623,
title = {Delocalization and stretch-bend mixing of the HOH bend in liquid water},
author = {Carpenter, William B. and Fournier, Joseph A. and Biswas, Rajib and Voth, Gregory A. and Tokmakoff, Andrei},
abstractNote = {Liquid water’s rich sub-picosecond vibrational dynamics arise from the interplay of different high- and low-frequency modes evolving in a strong yet fluctuating hydrogen bond network. Recent studies of the OH stretching excitations of H2O indicate that they are delocalized over several molecules, raising questions about whether the bending vibrations are similarly delocalized. In this paper, we take advantage of an improved 50 fs time-resolution and broadband infrared (IR) spectroscopy to interrogate the 2D IR lineshape and spectral dynamics of the HOH bending vibration of liquid H2O. Indications of strong bend-stretch coupling are observed in early time 2D IR spectra through a broad excited state absorption that extends from 1500 cm-1 to beyond 1900 cm-1, which corresponds to transitions from the bend to the bend overtone and OH stretching band between 3150 and 3550 cm-1. Pump-probe measurements reveal a fast 180 fs vibrational relaxation time, which results in a hot-ground state spectrum that is the same as observed for water IR excitation at any other frequency. The fastest dynamical time scale is 80 fs for the polarization anisotropy decay, providing evidence for the delocalized or excitonic character of the bend. Finally, normal mode analysis conducted on water clusters extracted from molecular dynamics simulations corroborate significant stretch-bend mixing and indicate delocalization of δHOH on 2-7 water molecules.},
doi = {10.1063/1.4987153},
journal = {Journal of Chemical Physics},
number = 8,
volume = 147,
place = {United States},
year = {2017},
month = {8}
}

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