We develop a new scheme for determining molecular partial atomic charges (PACs) with external electrostatic potential (ESP) closely mimicking that of the molecule. The PACs are the "minimal corrections" to a reference-set of PACs necessary for reproducing exactly the tensor components of the Cartesian zero- first- and second- molecular electrostatic multipoles. We evaluate the quality of ESP reproduction when "minimally correcting" (MC) Mulliken, Hirshfeld or iterated-Hirshfeld reference PACs. In all these cases the MC-PACs significantly improve the ESP while preserving the reference PACs' invariance under the molecular symmetry operations. When iterative-Hirshfeld PACs are used as reference the MC-PACs yield ESPs of comparable quality to those of the ChElPG charge fitting method.
MACE-POLAR-1: A Polarisable Electrostatic Foundation Model for Molecular Chemistry
Engineering Laboratory, University of Cambridge, Trumpington St, Cambridge, UK；Yusuf Hamied Department of Chemistry, University of Cambridge, Lensfield Road, Cambridge, UK；Cavendish Laboratory, University of Cambridge, J. J. Thomson Avenue, Cambridge, UK；Scientific Computing Department, Science；Technology Facilities Council, Daresbury Laboratory, Keckwick Lane, Daresbury WA4 4AD, UK；Department of Physics；Astronomy, University College London, 7-19 Gordon St, London WC1H 0AH, United Kingdom；Initiative for Computational Catalysis, Flatiron Institute, 160 5th Avenue, New York, NY 10010；School of Natural；Environmental Sciences, Newcastle University, Newcastle upon Tyne, UK；Max Planck Institute for Polymer Research, Ackermannweg 10, Mainz, Germany
Manipulation of Diatomic Molecules with 'Oriented External Electric Fields': Linear Correlations in Atomic Properties Lead to Non-Linear Molecular Responses
