title: A Universal and Straightforward Approach to Include Penetration Effects in Electrostatic Interaction Energy Estimation.
abstract: To compensate for the lack of the explicit treatment of charge penetration in classical force fields, we propose a new charge-distribution model based on a promolecule augmented with point charges (aug-PROmol). It relies on a superposition of spherical atomic electron densities obtained for each chemical element from SCF energy optimized atomic orbitals. Atomic densities are further rescaled by partial point charges computed from fits to the molecular electrostatic potential. Aug-PROmol was tested on the S66 benchmark dataset extended to nonequilibrium geometries (J. Chem. Theory Comput., 2011, 7, 3466). The model does not need any additional parametrization other than point charges. Despite its simplicity, aug-PROmol approximates the electrostatic energy with good agreement (RMSE=0.76 kcal mol(-1) to DFT-SAPT with B3LYP/aug-cc-pVTZ).
authors.affiliation: Department of Chemistry, Biological and Chemical Research Centre, University of Warsaw, ul. Żwirki i Wigury 101, 02-089, Warszawa, Poland.
authors.forename: Sławomir A
authors.identifier: http://orcid.org/0000-0001-5028-0221
authors.initials: SA
authors.lastname: Bojarowski
authors.affiliation: Department of Chemistry, Biological and Chemical Research Centre, University of Warsaw, ul. Żwirki i Wigury 101, 02-089, Warszawa, Poland.
authors.forename: Prashant
authors.identifier: http://orcid.org/0000-0001-5154-1059
authors.initials: P
authors.lastname: Kumar
authors.affiliation: Department of Chemistry, Biological and Chemical Research Centre, University of Warsaw, ul. Żwirki i Wigury 101, 02-089, Warszawa, Poland. pdomin@chem.uw.edu.pl.
authors.forename: Paulina M
authors.identifier: http://orcid.org/0000-0002-1466-1243
authors.initials: PM
authors.lastname: Dominiak
keywords: Coulomb interaction energies; charge penetration; computational chemistry; electron density; force field models