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Expanding the scope of density derived electrostatic and chemical charge partitioning to thousands of atoms

Expanding the scope of density derived electrostatic and chemical charge partitioning to thousands of atoms
Expanding the scope of density derived electrostatic and chemical charge partitioning to thousands of atoms
The density derived electrostatic and chemical (DDEC/c3) method is implemented into the onetep program to compute net atomic charges (NACs), as well as higher-order atomic multipole moments, of molecules, dense solids, nanoclusters, liquids, and biomolecules using linear-scaling density functional theory (DFT) in a distributed memory parallel computing environment. For a >1000 atom model of the oxygenated myoglobin protein, the DDEC/c3 net charge of the adsorbed oxygen molecule is approximately ?1e (in agreement with the Weiss model) using a dynamical mean field theory treatment of the iron atom, but much smaller in magnitude when using the generalized gradient approximation. For GaAs semiconducting nanorods, the system dipole moment using the DDEC/c3 NACs is about 5% higher in magnitude than the dipole computed directly from the quantum mechanical electron density distribution, and the DDEC/c3 NACs reproduce the electrostatic potential to within approximately 0.1 V on the nanorod’s solvent-accessible surface. As examples of conducting materials, we study (i) a 55-atom Pt cluster with an adsorbed CO molecule and (ii) the dense solids Mo2C and Pd3V. Our results for solid Mo2C and Pd3V confirm the necessity of a constraint enforcing exponentially decaying electron density in the tails of buried atoms.
1549-9618
5377-5390
Lee, Louis P.
7e11b32f-b117-4ad0-a6f1-18109b47b89f
Limas, Nidia Gabaldon
3015954d-4899-4b84-9f32-45c81167da57
Cole, Daniel J.
cb208a53-13ef-4871-b59b-6373abaadc39
Payne, Mike C.
abb730ea-f683-4bec-a7e0-766f0a180a05
Skylaris, Chris-Kriton
8f593d13-3ace-4558-ba08-04e48211af61
Manz, Thomas A.
bae12b24-3635-4ca0-a61b-5f8bc6d19c6b
Lee, Louis P.
7e11b32f-b117-4ad0-a6f1-18109b47b89f
Limas, Nidia Gabaldon
3015954d-4899-4b84-9f32-45c81167da57
Cole, Daniel J.
cb208a53-13ef-4871-b59b-6373abaadc39
Payne, Mike C.
abb730ea-f683-4bec-a7e0-766f0a180a05
Skylaris, Chris-Kriton
8f593d13-3ace-4558-ba08-04e48211af61
Manz, Thomas A.
bae12b24-3635-4ca0-a61b-5f8bc6d19c6b

Lee, Louis P., Limas, Nidia Gabaldon, Cole, Daniel J., Payne, Mike C., Skylaris, Chris-Kriton and Manz, Thomas A. (2014) Expanding the scope of density derived electrostatic and chemical charge partitioning to thousands of atoms. Journal of Chemical Theory and Computation, 10 (12), 5377-5390. (doi:10.1021/ct500766v). (PMID:26583221)

Record type: Article

Abstract

The density derived electrostatic and chemical (DDEC/c3) method is implemented into the onetep program to compute net atomic charges (NACs), as well as higher-order atomic multipole moments, of molecules, dense solids, nanoclusters, liquids, and biomolecules using linear-scaling density functional theory (DFT) in a distributed memory parallel computing environment. For a >1000 atom model of the oxygenated myoglobin protein, the DDEC/c3 net charge of the adsorbed oxygen molecule is approximately ?1e (in agreement with the Weiss model) using a dynamical mean field theory treatment of the iron atom, but much smaller in magnitude when using the generalized gradient approximation. For GaAs semiconducting nanorods, the system dipole moment using the DDEC/c3 NACs is about 5% higher in magnitude than the dipole computed directly from the quantum mechanical electron density distribution, and the DDEC/c3 NACs reproduce the electrostatic potential to within approximately 0.1 V on the nanorod’s solvent-accessible surface. As examples of conducting materials, we study (i) a 55-atom Pt cluster with an adsorbed CO molecule and (ii) the dense solids Mo2C and Pd3V. Our results for solid Mo2C and Pd3V confirm the necessity of a constraint enforcing exponentially decaying electron density in the tails of buried atoms.

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e-pub ahead of print date: 3 November 2014
Published date: 9 December 2014
Organisations: Computational Systems Chemistry

Identifiers

Local EPrints ID: 396122
URI: http://eprints.soton.ac.uk/id/eprint/396122
ISSN: 1549-9618
PURE UUID: 30ea7145-8904-42ab-abd7-ebe7208db58a
ORCID for Chris-Kriton Skylaris: ORCID iD orcid.org/0000-0003-0258-3433

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Date deposited: 02 Jun 2016 13:29
Last modified: 29 Oct 2019 01:48

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