Polarizable Molecules in the Vibrational Spectroscopy of Water

We examine the role of electronic polarizability in water on short (tens of femtoseconds), intermediate (hundreds of femtoseconds), and long (≈1 ps) time scales by comparing molecular dynamics results to experimental data for vibrational spectroscopy of HOD in liquid D2O. Because the OH absorption f...

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Published inProceedings of the National Academy of Sciences - PNAS Vol. 102; no. 33; pp. 11611 - 11616
Main Authors Harder, Edward, Eaves, Joel D., Tokmakoff, Andrei, Berne, B. J.
Format Journal Article
LanguageEnglish
Published United States National Academy of Sciences 16.08.2005
National Acad Sciences
Subjects
Absorption spectra
Chemistry
Degrees of freedom
Electric fields
Liquids
Modeling
Molecular biology
Molecules
Physical Sciences
Potential energy
Simulations
Spectrum analysis
Vapor phases
Vibration
Vibration analysis
Water
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Summary:We examine the role of electronic polarizability in water on short (tens of femtoseconds), intermediate (hundreds of femtoseconds), and long (≈1 ps) time scales by comparing molecular dynamics results to experimental data for vibrational spectroscopy of HOD in liquid D2O. Because the OH absorption frequency is sensitive to the details of the atomic forces experienced in the liquid, our results provide important quantitative comparisons for several popular empirical water potentials. When compared with their fixed-charge counterparts, the polarizable models give similar slower long time constants for the decay of vibrational correlations and reorientational motion that is in better agreement with experiments. Polarizable potentials yield qualitatively dissimilar predictions for frequency fluctuations and transition dipole moment fluctuations at equilibrium. Models that confine the polarizability to the plane of the molecule (i.e., TIP4P-FQ) overestimate the width of the distribution describing frequency fluctuations by more than a factor of two. These models also underestimate the amplitude of the hydrogen-bond stretch at 170 cm-1. A potential that has both an out-of-plane polarization and fluctuating charges, POL5-TZ, compares best with experiments. We interpret our findings in terms of microscopic dynamics and make suggestions that may improve the quality of emerging polarizable force fields for water.
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To whom correspondence should be addressed. E-mail: bb8@columbia.edu.
Contributed by B. J. Berne, June 21, 2005
E.H. and J.D.E. contributed equally to this work.
Abbreviations: MD, molecular dynamics; TDM, transition dipole moment; DC, Dang–Chang; FWHM, full width at half maximum.
Author contributions: E.H. and J.D.E. performed research; E.H., J.D.E., and B.J.B. wrote the paper; and A.T. initiated collaboration.
ISSN:0027-8424
1091-6490
DOI:10.1073/pnas.0505206102