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Electrostatic interactions in finite systems treated with periodic boundary conditions: application to linear-scaling density functional theory

Electrostatic interactions in finite systems treated with periodic boundary conditions: application to linear-scaling density functional theory
Electrostatic interactions in finite systems treated with periodic boundary conditions: application to linear-scaling density functional theory
We present a comparison of methods for treating the electrostatic interactions of finite, isolated systems within periodic boundary conditions (PBCs), within density functional theory (DFT), with particular emphasis on linear-scaling (LS) DFT. Often, PBCs are not physically realistic but are an unavoidable consequence of the choice of basis set and the efficacy of using Fourier transforms to compute the Hartree potential. In such cases the effects of PBCs on the calculations need to be avoided, so that the results obtained represent the open rather than the periodic boundary. The very large systems encountered in LS-DFT make the demands of the supercell approximation for isolated systems more difficult to manage, and we show cases where the open boundary (infinite cell) result cannot be obtained from extrapolation of calculations from periodic cells of increasing size. We discuss, implement, and test three very different approaches for overcoming or circumventing the effects of PBCs: truncation of the Coulomb interaction combined with padding of the simulation cell, approaches based on the minimum image convention, and the explicit use of open boundary conditions (OBCs). We have implemented these approaches in the ONETEP LS-DFT program and applied them to a range of systems, including a polar nanorod and a protein. We compare their accuracy, complexity, and rate of convergence with simulation cell size. We demonstrate that corrective approaches within PBCs can achieve the OBC result more efficiently and accurately than pure OBC approaches
0021-9606
204103-[17pp]
Hine, Nicholas D.M.
6acbd836-08cc-45fe-96aa-5274a388e05d
Dziedzic, Jacek
658f5c6d-7880-4b3b-a4d7-0e863ead9422
Haynes, Peter D.
7672b51a-83dc-417e-9ffc-7eb9f8c0334c
Skylaris, Chris-Kriton
8f593d13-3ace-4558-ba08-04e48211af61
Hine, Nicholas D.M.
6acbd836-08cc-45fe-96aa-5274a388e05d
Dziedzic, Jacek
658f5c6d-7880-4b3b-a4d7-0e863ead9422
Haynes, Peter D.
7672b51a-83dc-417e-9ffc-7eb9f8c0334c
Skylaris, Chris-Kriton
8f593d13-3ace-4558-ba08-04e48211af61

Hine, Nicholas D.M., Dziedzic, Jacek, Haynes, Peter D. and Skylaris, Chris-Kriton (2011) Electrostatic interactions in finite systems treated with periodic boundary conditions: application to linear-scaling density functional theory. The Journal of Chemical Physics, 135 (20), 204103-[17pp]. (doi:10.1063/1.3662863).

Record type: Article

Abstract

We present a comparison of methods for treating the electrostatic interactions of finite, isolated systems within periodic boundary conditions (PBCs), within density functional theory (DFT), with particular emphasis on linear-scaling (LS) DFT. Often, PBCs are not physically realistic but are an unavoidable consequence of the choice of basis set and the efficacy of using Fourier transforms to compute the Hartree potential. In such cases the effects of PBCs on the calculations need to be avoided, so that the results obtained represent the open rather than the periodic boundary. The very large systems encountered in LS-DFT make the demands of the supercell approximation for isolated systems more difficult to manage, and we show cases where the open boundary (infinite cell) result cannot be obtained from extrapolation of calculations from periodic cells of increasing size. We discuss, implement, and test three very different approaches for overcoming or circumventing the effects of PBCs: truncation of the Coulomb interaction combined with padding of the simulation cell, approaches based on the minimum image convention, and the explicit use of open boundary conditions (OBCs). We have implemented these approaches in the ONETEP LS-DFT program and applied them to a range of systems, including a polar nanorod and a protein. We compare their accuracy, complexity, and rate of convergence with simulation cell size. We demonstrate that corrective approaches within PBCs can achieve the OBC result more efficiently and accurately than pure OBC approaches

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Published date: November 2011
Organisations: Computational Systems Chemistry

Identifiers

Local EPrints ID: 336975
URI: https://eprints.soton.ac.uk/id/eprint/336975
ISSN: 0021-9606
PURE UUID: 040d2fbe-9451-4043-b97b-f78b8656355b
ORCID for Chris-Kriton Skylaris: ORCID iD orcid.org/0000-0003-0258-3433

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Date deposited: 12 Apr 2012 14:11
Last modified: 17 Jul 2018 00:32

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