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Title: Direct computation of parameters for accurate polarizable force fields

We present an improved electronic linear response model to incorporate polarization and charge-transfer effects in polarizable force fields. This model is a generalization of the Atom-Condensed Kohn-Sham Density Functional Theory (DFT), approximated to second order (ACKS2): it can now be defined with any underlying variational theory (next to KS-DFT) and it can include atomic multipoles and off-center basis functions. Parameters in this model are computed efficiently as expectation values of an electronic wavefunction, obviating the need for their calibration, regularization, and manual tuning. In the limit of a complete density and potential basis set in the ACKS2 model, the linear response properties of the underlying theory for a given molecular geometry are reproduced exactly. A numerical validation with a test set of 110 molecules shows that very accurate models can already be obtained with fluctuating charges and dipoles. These features greatly facilitate the development of polarizable force fields.
Authors:
;  [1] ;  [2]
  1. Center for Molecular Modeling (CMM), Member of the QCMM Ghent–Brussels Alliance, Ghent University, Technologiepark 903, B9000 Ghent (Belgium)
  2. Department of Chemistry and Chemical Biology, McMaster University, 1280 Main Street West, Hamilton, Ontario L8S 4M1 (Canada)
Publication Date:
OSTI Identifier:
22415372
Resource Type:
Journal Article
Resource Relation:
Journal Name: Journal of Chemical Physics; Journal Volume: 141; Journal Issue: 19; Other Information: (c) 2014 AIP Publishing LLC; Country of input: International Atomic Energy Agency (IAEA)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY; 74 ATOMIC AND MOLECULAR PHYSICS; CALIBRATION; DENSITY; DENSITY FUNCTIONAL METHOD; DIPOLES; POLARIZATION; VALIDATION; WAVE FUNCTIONS