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Title: Quantum mechanical force field for water with explicit electronic polarization

Abstract

A quantum mechanical force field (QMFF) for water is described. Unlike traditional approaches that use quantum mechanical results and experimental data to parameterize empirical potential energy functions, the present QMFF uses a quantum mechanical framework to represent intramolecular and intermolecular interactions in an entire condensed-phase system. In particular, the internal energy terms used in molecular mechanics are replaced by a quantum mechanical formalism that naturally includes electronic polarization due to intermolecular interactions and its effects on the force constants of the intramolecular force field. As a quantum mechanical force field, both intermolecular interactions and the Hamiltonian describing the individual molecular fragments can be parameterized to strive for accuracy and computational efficiency. In this work, we introduce a polarizable molecular orbital model Hamiltonian for water and for oxygen- and hydrogen-containing compounds, whereas the electrostatic potential responsible for intermolecular interactions in the liquid and in solution is modeled by a three-point charge representation that realistically reproduces the total molecular dipole moment and the local hybridization contributions. The present QMFF for water, which is called the XP3P (explicit polarization with three-point-charge potential) model, is suitable for modeling both gas-phase clusters and liquid water. The paper demonstrates the performance of the XP3P model formore » water and proton clusters and the properties of the pure liquid from about 900 × 10{sup 6} self-consistent-field calculations on a periodic system consisting of 267 water molecules. The unusual dipole derivative behavior of water, which is incorrectly modeled in molecular mechanics, is naturally reproduced as a result of an electronic structural treatment of chemical bonding by XP3P. We anticipate that the XP3P model will be useful for studying proton transport in solution and solid phases as well as across biological ion channels through membranes.« less

Authors:
; ; ; ;  [1]
  1. Department of Chemistry and Supercomputing Institute, University of Minnesota, 207 Pleasant Street, SE, Minneapolis, Minnesota 55455-0431 (United States)
Publication Date:
OSTI Identifier:
22220485
Resource Type:
Journal Article
Journal Name:
Journal of Chemical Physics
Additional Journal Information:
Journal Volume: 139; Journal Issue: 5; Other Information: (c) 2013 AIP Publishing LLC; Country of input: International Atomic Energy Agency (IAEA); Journal ID: ISSN 0021-9606
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY; 75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND SUPERFLUIDITY; ACCURACY; DIPOLE MOMENTS; DIPOLES; EFFICIENCY; ELECTRIC MOMENTS; ELECTRONIC STRUCTURE; HAMILTONIANS; INTERACTIONS; LIQUIDS; MEMBRANES; MOLECULAR CLUSTERS; MOLECULAR DYNAMICS METHOD; PERIODIC SYSTEM; POINT CHARGE; POLARIZATION; POTENTIAL ENERGY; SIMULATION; SOLUTIONS

Citation Formats

Han, Jaebeom, Mazack, Michael J. M., Zhang, Peng, Truhlar, Donald G., and Gao, Jiali. Quantum mechanical force field for water with explicit electronic polarization. United States: N. p., 2013. Web. doi:10.1063/1.4816280.
Han, Jaebeom, Mazack, Michael J. M., Zhang, Peng, Truhlar, Donald G., & Gao, Jiali. Quantum mechanical force field for water with explicit electronic polarization. United States. https://doi.org/10.1063/1.4816280
Han, Jaebeom, Mazack, Michael J. M., Zhang, Peng, Truhlar, Donald G., and Gao, Jiali. Wed . "Quantum mechanical force field for water with explicit electronic polarization". United States. https://doi.org/10.1063/1.4816280.
@article{osti_22220485,
title = {Quantum mechanical force field for water with explicit electronic polarization},
author = {Han, Jaebeom and Mazack, Michael J. M. and Zhang, Peng and Truhlar, Donald G. and Gao, Jiali},
abstractNote = {A quantum mechanical force field (QMFF) for water is described. Unlike traditional approaches that use quantum mechanical results and experimental data to parameterize empirical potential energy functions, the present QMFF uses a quantum mechanical framework to represent intramolecular and intermolecular interactions in an entire condensed-phase system. In particular, the internal energy terms used in molecular mechanics are replaced by a quantum mechanical formalism that naturally includes electronic polarization due to intermolecular interactions and its effects on the force constants of the intramolecular force field. As a quantum mechanical force field, both intermolecular interactions and the Hamiltonian describing the individual molecular fragments can be parameterized to strive for accuracy and computational efficiency. In this work, we introduce a polarizable molecular orbital model Hamiltonian for water and for oxygen- and hydrogen-containing compounds, whereas the electrostatic potential responsible for intermolecular interactions in the liquid and in solution is modeled by a three-point charge representation that realistically reproduces the total molecular dipole moment and the local hybridization contributions. The present QMFF for water, which is called the XP3P (explicit polarization with three-point-charge potential) model, is suitable for modeling both gas-phase clusters and liquid water. The paper demonstrates the performance of the XP3P model for water and proton clusters and the properties of the pure liquid from about 900 × 10{sup 6} self-consistent-field calculations on a periodic system consisting of 267 water molecules. The unusual dipole derivative behavior of water, which is incorrectly modeled in molecular mechanics, is naturally reproduced as a result of an electronic structural treatment of chemical bonding by XP3P. We anticipate that the XP3P model will be useful for studying proton transport in solution and solid phases as well as across biological ion channels through membranes.},
doi = {10.1063/1.4816280},
url = {https://www.osti.gov/biblio/22220485}, journal = {Journal of Chemical Physics},
issn = {0021-9606},
number = 5,
volume = 139,
place = {United States},
year = {2013},
month = {8}
}