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Electrostatic interactions in finite systems treated with periodic boundary conditions : application to linear-scaling density functional theory
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Hine, Nicholas, 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. Journal of Chemical Physics, 135 (20). 204103 . doi:10.1063/1.3662863 ISSN 0021-9606.
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Official URL: http://dx.doi.org/10.1063/1.3662863
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.
Item Type: | Journal Article | ||||
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Subjects: | Q Science > QD Chemistry | ||||
Divisions: | Faculty of Science, Engineering and Medicine > Science > Physics | ||||
Library of Congress Subject Headings (LCSH): | Density functionals, Fourier transformations, Quantum theory, Boundary value problems, Mathematical physics | ||||
Journal or Publication Title: | Journal of Chemical Physics | ||||
Publisher: | American Institute of Physics | ||||
ISSN: | 0021-9606 | ||||
Official Date: | 2011 | ||||
Dates: |
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Volume: | 135 | ||||
Number: | 20 | ||||
Article Number: | 204103 | ||||
DOI: | 10.1063/1.3662863 | ||||
Status: | Peer Reviewed | ||||
Publication Status: | Published | ||||
Date of first compliant deposit: | 1 April 2016 | ||||
Date of first compliant Open Access: | 1 April 2016 | ||||
Funder: | Engineering and Physical Sciences Research Council (EPSRC) | ||||
Grant number: | EP/F010974/1, EP/G05567X/1, EP/G055882/1 |
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