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Title: Differences in the Vibrational Dynamics of H2O and D2O: Observation of Symmetric and Antisymmetric Stretching Vibrations in Heavy Water

Abstract

Water’s ability to donate and accept hydrogen bonds leads to unique and complex collective dynamical phenomena associated with its hydrogen-bond network. It is appreciated that the vibrations governing liquid water’s molecular dynamics are delocalized, with nuclear motion evolving coherently over the span of several molecules. Using two-dimensional infrared spectroscopy, we have found that the nuclear motions of heavy water, D2O, are qualitatively different than those of H2O. The nonlinear spectrum of liquid D2O reveals distinct O–D stretching resonances, in contrast to H2O. Furthermore, our data indicates that condensed-phase O–D vibrations have a different character than those in the gas phase, which we understand in terms of weakly delocalized symmetric and antisymmetric stretching vibrations. Finally, this difference in molecular dynamics reflects the shift in the balance between intra- and intermolecular couplings upon deuteration, an effect which can be understood in terms of the anharmonicity of the nuclear potential energy surface.

Authors:
 [1];  [2];  [3];  [2];  [3];  [2]
+ Show Author Affiliations
  1. Massachusetts Inst. of Technology (MIT), Cambridge, MA (United States); Univ. of Chicago, IL (United States)
  2. Univ. of Chicago, IL (United States)
  3. Emory Univ., Atlanta, GA (United States)
Publication Date:
Research Org.:
Univ. of Chicago, IL (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences, and Biosciences Division; National Science Foundation (NSF)
OSTI Identifier:
1600626
Grant/Contract Number:  
SC0014305; CHE-1463552
Resource Type:
Accepted Manuscript
Journal Name:
Journal of Physical Chemistry Letters
Additional Journal Information:
Journal Volume: 7; Journal Issue: 10; Journal ID: ISSN 1948-7185
Publisher:
American Chemical Society
Country of Publication:
United States
Language:
English
Subject:
74 ATOMIC AND MOLECULAR PHYSICS; molecules; oscillation; infrared light; molecular structure; polarization

Citation Formats

De Marco, Luigi, Carpenter, William, Liu, Hanchao, Biswas, Rajib, Bowman, Joel M., and Tokmakoff, Andrei. Differences in the Vibrational Dynamics of H2O and D2O: Observation of Symmetric and Antisymmetric Stretching Vibrations in Heavy Water. United States: N. p., 2016. Web. doi:10.1021/acs.jpclett.6b00668.
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De Marco, Luigi, Carpenter, William, Liu, Hanchao, Biswas, Rajib, Bowman, Joel M., & Tokmakoff, Andrei. Differences in the Vibrational Dynamics of H2O and D2O: Observation of Symmetric and Antisymmetric Stretching Vibrations in Heavy Water. United States. https://doi.org/10.1021/acs.jpclett.6b00668
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De Marco, Luigi, Carpenter, William, Liu, Hanchao, Biswas, Rajib, Bowman, Joel M., and Tokmakoff, Andrei. Tue . "Differences in the Vibrational Dynamics of H2O and D2O: Observation of Symmetric and Antisymmetric Stretching Vibrations in Heavy Water". United States. https://doi.org/10.1021/acs.jpclett.6b00668. https://www.osti.gov/servlets/purl/1600626.
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@article{osti_1600626,
title = {Differences in the Vibrational Dynamics of H2O and D2O: Observation of Symmetric and Antisymmetric Stretching Vibrations in Heavy Water},
author = {De Marco, Luigi and Carpenter, William and Liu, Hanchao and Biswas, Rajib and Bowman, Joel M. and Tokmakoff, Andrei},
abstractNote = {Water’s ability to donate and accept hydrogen bonds leads to unique and complex collective dynamical phenomena associated with its hydrogen-bond network. It is appreciated that the vibrations governing liquid water’s molecular dynamics are delocalized, with nuclear motion evolving coherently over the span of several molecules. Using two-dimensional infrared spectroscopy, we have found that the nuclear motions of heavy water, D2O, are qualitatively different than those of H2O. The nonlinear spectrum of liquid D2O reveals distinct O–D stretching resonances, in contrast to H2O. Furthermore, our data indicates that condensed-phase O–D vibrations have a different character than those in the gas phase, which we understand in terms of weakly delocalized symmetric and antisymmetric stretching vibrations. Finally, this difference in molecular dynamics reflects the shift in the balance between intra- and intermolecular couplings upon deuteration, an effect which can be understood in terms of the anharmonicity of the nuclear potential energy surface.},
doi = {10.1021/acs.jpclett.6b00668},
journal = {Journal of Physical Chemistry Letters},
number = 10,
volume = 7,
place = {United States},
year = {Tue Apr 26 00:00:00 EDT 2016},
month = {Tue Apr 26 00:00:00 EDT 2016}
}
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https://doi.org/10.1021/acs.jpclett.6b00668
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    Works referencing / citing this record:

    Femtosecond infrared pump–stimulated Raman probe spectroscopy: the first application of the method to studies of vibrational relaxation pathways in the liquid HDO/D 2 O system
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