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An efficient water force field calibrated against intermolecular THz and Raman spectra


Sidler, David; Meuwly, Markus; Hamm, Peter (2018). An efficient water force field calibrated against intermolecular THz and Raman spectra. Journal of Chemical Physics, 148(24):244504.

Abstract

A polarizable water model is presented which has been calibrated against experimental THz and Raman spectra of bulk water. These low-frequency spectra directly probe the dynamics, and thereby intermolecular interactions, on time scales relevant to molecular motions. The model is based on the TL4P force field developed recently by Tavan and co-workers [J. Phys. Chem. B 117, 9486 (2013)], which has been designed to be transferable between different environments; in particular, to correctly describe the electrostatic properties of both the isolated water molecule in the gas-phase and the liquid water at ambient conditions. Following this design philosophy, TL4P was amended with charge transfer across hydrogen-bonded dimers as well as an anisotropic polarizability in order to correctly reproduce the THz and Raman spectra. The thermodynamic and structural properties of the new model are of equal quality as those of TL4P, and at the same time, an almost quantitative agreement with the spectroscopic data could be achieved. Since TL4P is a rigid model with a single polarizable site, it is computationally very efficient, while the numerical overhead for the addition of charge transfer and the anisotropic polarizability is minor. Overall, the model is expected to be well suited for, e.g., large scale simulations of 2D-Raman-THz spectra or biomolecular simulations. Published by AIP Publishing.

Abstract

A polarizable water model is presented which has been calibrated against experimental THz and Raman spectra of bulk water. These low-frequency spectra directly probe the dynamics, and thereby intermolecular interactions, on time scales relevant to molecular motions. The model is based on the TL4P force field developed recently by Tavan and co-workers [J. Phys. Chem. B 117, 9486 (2013)], which has been designed to be transferable between different environments; in particular, to correctly describe the electrostatic properties of both the isolated water molecule in the gas-phase and the liquid water at ambient conditions. Following this design philosophy, TL4P was amended with charge transfer across hydrogen-bonded dimers as well as an anisotropic polarizability in order to correctly reproduce the THz and Raman spectra. The thermodynamic and structural properties of the new model are of equal quality as those of TL4P, and at the same time, an almost quantitative agreement with the spectroscopic data could be achieved. Since TL4P is a rigid model with a single polarizable site, it is computationally very efficient, while the numerical overhead for the addition of charge transfer and the anisotropic polarizability is minor. Overall, the model is expected to be well suited for, e.g., large scale simulations of 2D-Raman-THz spectra or biomolecular simulations. Published by AIP Publishing.

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Additional indexing

Item Type:Journal Article, refereed, original work
Communities & Collections:07 Faculty of Science > Department of Chemistry
Dewey Decimal Classification:540 Chemistry
Uncontrolled Keywords:Physical and Theoretical Chemistry, General Physics and Astronomy
Language:English
Date:28 June 2018
Deposited On:05 Feb 2019 13:30
Last Modified:05 Feb 2019 13:34
Publisher:American Institute of Physics
ISSN:0021-9606
OA Status:Closed
Publisher DOI:https://doi.org/10.1063/1.5037062
Project Information:
  • : FunderSwiss National Science Foundation (SNF) through the NCCR MUST
  • : Grant ID
  • : Project Title

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Embargo till: 2019-06-25