DOI: 10.1126/science.1087251. Ultrafast Hydrogen-Bond Dynamics in the Infrared Spectroscopy of Water

Ultrafast Hydrogen-Bond Dynamics in the Infrared Spectroscopy of Water

10.1126/science.1087251

Crossref journal-article

American Association for the Advancement of Science (AAAS)

Science (221)

Abstract

We investigated rearrangements of the hydrogen-bond network in water by measuring fluctuations in the OH-stretching frequency of HOD in liquid D 2 O with femtosecond infrared spectroscopy. Using simulations of an atomistic model of water, we relate these frequency fluctuations to intermolecular dynamics. The model reveals that OH frequency shifts arise from changes in the molecular electric field that acts on the proton. At short times, vibrational dephasing reflects an underdamped oscillation of the hydrogen bond with a period of 170 femtoseconds. At longer times, vibrational correlations decay on a 1.2-picosecond time scale because of collective structural reorganizations.

Bibliography

Fecko, C. J., Eaves, J. D., Loparo, J. J., Tokmakoff, A., & Geissler, P. L. (2003). Ultrafast Hydrogen-Bond Dynamics in the Infrared Spectroscopy of Water. Science, 301(5640), 1698â1702.

Authors 5

C. J. Fecko (first)
J. D. Eaves (additional)
J. J. Loparo (additional)
A. Tokmakoff (additional)
P. L. Geissler (additional)

References 30 Referenced 904

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We thank J. L. Skinner for many helpful conversations and both J. L. Skinner and J. T. Hynes for sending preprints of their work. Supported by Basic Energy Sciences of the U.S. Department of Energy (grant no. DE-FG02-99ER14988) the NSF Laser Research Facility at MIT (grant no. CHE-0111370) and the David and Lucile Packard Foundation. P.L.G. is an MIT Science Fellow. J.J.L. thanks the U.S. Department of Defense for a National Defense Science and Engineering Graduate fellowship.

Dates

Type	When
Created	21 years, 11 months ago (Sept. 18, 2003, 3:38 p.m.)
Deposited	1 year, 7 months ago (Jan. 9, 2024, 11:41 p.m.)
Indexed	7 hours, 36 minutes ago (Aug. 29, 2025, 6 a.m.)
Issued	21 years, 11 months ago (Sept. 19, 2003)
Published	21 years, 11 months ago (Sept. 19, 2003)
Published Print	21 years, 11 months ago (Sept. 19, 2003)

Funders 0

None

BibTeX

@article{Fecko_2003, title={Ultrafast Hydrogen-Bond Dynamics in the Infrared Spectroscopy of Water}, volume={301}, ISSN={1095-9203}, url={http://dx.doi.org/10.1126/science.1087251}, DOI={10.1126/science.1087251}, number={5640}, journal={Science}, publisher={American Association for the Advancement of Science (AAAS)}, author={Fecko, C. J. and Eaves, J. D. and Loparo, J. J. and Tokmakoff, A. and Geissler, P. L.}, year={2003}, month=sep, pages={1698–1702} }

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