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Title: Polarizable charge equilibration model for predicting accurate electrostatic interactions in molecules and solids

Journal Article · · Journal of Chemical Physics
DOI:https://doi.org/10.1063/1.4978891· OSTI ID:1465950
 [1];  [1]; ORCiD logo [1];  [1]
  1. California Inst. of Technology (CalTech), Pasadena, CA (United States). Materials and Process Simulation Center
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Electrostatic interactions play a critical role in determining the properties, structures, and dynamics of chemical, biochemical, and material systems. These interactions are described well at the level of quantum mechanics (QM) but not so well for the various models used in force field simulations of these systems. In this paper, we propose and validate a new general methodology, denoted PQEq, to predict rapidly and dynamically the atomic charges and polarization underlying the electrostatic interactions. Here the polarization is described using an atomic sized Gaussian shaped electron density that can polarize away from the core in response to internal and external electric fields, while at the same time adjusting the charge on each core (described as a Gaussian function) so as to achieve a constant chemical potential across all atoms of the system. The parameters for PQEq are derived from experimental atomic properties of all elements up to Nobelium (atomic no. = 102). Additionally, we validate PQEq by comparing to QM interaction energy as probe dipoles are brought along various directions up to 30 molecules containing H, C, N, O, F, Si, P, S, and Cl atoms. We find that PQEq predicts interaction energies in excellent agreement with QM, much better than other common charge models such as obtained from QM using Mulliken or ESP charges and those from standard force fields (OPLS and AMBER). Since PQEq increases the accuracy of electrostatic interactions and the response to external electric fields, we expect that PQEq will be useful for a large range of applications including ligand docking to proteins, catalytic reactions, electrocatalysis, ferroelectrics, and growth of ceramics and films, where it could be incorporated into standard force fields as OPLS, AMBER, CHARMM, Dreiding, ReaxFF, and UFF.

Research Organization:
California Institute of Technology (CalTech), Pasadena, CA (United States)
Sponsoring Organization:
USDOE Office of Science (SC)
Grant/Contract Number:
SC0004993
OSTI ID:
1465950
Journal Information:
Journal of Chemical Physics, Vol. 146, Issue 12; ISSN 0021-9606
Publisher:
American Institute of Physics (AIP)Copyright Statement
Country of Publication:
United States
Language:
English
Citation Metrics:
Cited by: 40 works
Citation information provided by
Web of Science

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Electronic transitions for a fully polarizable QM/MM approach based on fluctuating charges and fluctuating dipoles: Linear and corrected linear response regimes journal November 2019
First-principles–based reaction kinetics from reactive molecular dynamics simulations: Application to hydrogen peroxide decomposition journal September 2018
First principles-based multiscale atomistic methods for input into first principles nonequilibrium transport across interfaces journal August 2018
Liquid water is a dynamic polydisperse branched polymer journal January 2019
Electronic Transitions for a Fully Polarizable QM/MM Approach Based on Fluctuating Charges and Fluctuating Dipoles: Linear and Corrected Linear Response Regimes text January 2019
Evaluating Charge Equilibration Methods To Generate Electrostatic Fields in Nanoporous Materials journal November 2018
Incorporating electronic information into Machine Learning potential energy surfaces via approaching the ground-state electronic energy as a function of atom-based electronic populations preprint January 2020
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