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Multipolar Ewald Methods, 1: Theory, Accuracy, and Performance
[Image: see text] The Ewald, Particle Mesh Ewald (PME), and Fast Fourier–Poisson (FFP) methods are developed for systems composed of spherical multipole moment expansions. A unified set of equations is derived that takes advantage of a spherical tensor gradient operator formalism in both real space...
Autores principales: | , , , |
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Formato: | Online Artículo Texto |
Lenguaje: | English |
Publicado: |
American
Chemical Society
2014
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Acceso en línea: | https://www.ncbi.nlm.nih.gov/pmc/articles/PMC4325605/ https://www.ncbi.nlm.nih.gov/pubmed/25691829 http://dx.doi.org/10.1021/ct5007983 |
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author | Giese, Timothy J. Panteva, Maria T. Chen, Haoyuan York, Darrin M. |
author_facet | Giese, Timothy J. Panteva, Maria T. Chen, Haoyuan York, Darrin M. |
author_sort | Giese, Timothy J. |
collection | PubMed |
description | [Image: see text] The Ewald, Particle Mesh Ewald (PME), and Fast Fourier–Poisson (FFP) methods are developed for systems composed of spherical multipole moment expansions. A unified set of equations is derived that takes advantage of a spherical tensor gradient operator formalism in both real space and reciprocal space to allow extension to arbitrary multipole order. The implementation of these methods into a novel linear-scaling modified “divide-and-conquer” (mDC) quantum mechanical force field is discussed. The evaluation times and relative force errors are compared between the three methods, as a function of multipole expansion order. Timings and errors are also compared within the context of the quantum mechanical force field, which encounters primary errors related to the quality of reproducing electrostatic forces for a given density matrix and secondary errors resulting from the propagation of the approximate electrostatics into the self-consistent field procedure, which yields a converged, variational, but nonetheless approximate density matrix. Condensed-phase simulations of an mDC water model are performed with the multipolar PME method and compared to an electrostatic cutoff method, which is shown to artificially increase the density of water and heat of vaporization relative to full electrostatic treatment. |
format | Online Article Text |
id | pubmed-4325605 |
institution | National Center for Biotechnology Information |
language | English |
publishDate | 2014 |
publisher | American
Chemical Society |
record_format | MEDLINE/PubMed |
spelling | pubmed-43256052015-12-27 Multipolar Ewald Methods, 1: Theory, Accuracy, and Performance Giese, Timothy J. Panteva, Maria T. Chen, Haoyuan York, Darrin M. J Chem Theory Comput [Image: see text] The Ewald, Particle Mesh Ewald (PME), and Fast Fourier–Poisson (FFP) methods are developed for systems composed of spherical multipole moment expansions. A unified set of equations is derived that takes advantage of a spherical tensor gradient operator formalism in both real space and reciprocal space to allow extension to arbitrary multipole order. The implementation of these methods into a novel linear-scaling modified “divide-and-conquer” (mDC) quantum mechanical force field is discussed. The evaluation times and relative force errors are compared between the three methods, as a function of multipole expansion order. Timings and errors are also compared within the context of the quantum mechanical force field, which encounters primary errors related to the quality of reproducing electrostatic forces for a given density matrix and secondary errors resulting from the propagation of the approximate electrostatics into the self-consistent field procedure, which yields a converged, variational, but nonetheless approximate density matrix. Condensed-phase simulations of an mDC water model are performed with the multipolar PME method and compared to an electrostatic cutoff method, which is shown to artificially increase the density of water and heat of vaporization relative to full electrostatic treatment. American Chemical Society 2014-12-27 2015-02-10 /pmc/articles/PMC4325605/ /pubmed/25691829 http://dx.doi.org/10.1021/ct5007983 Text en Copyright © 2014 American Chemical Society This is an open access article published under an ACS AuthorChoice License (http://pubs.acs.org/page/policy/authorchoice_termsofuse.html) , which permits copying and redistribution of the article or any adaptations for non-commercial purposes. |
spellingShingle | Giese, Timothy J. Panteva, Maria T. Chen, Haoyuan York, Darrin M. Multipolar Ewald Methods, 1: Theory, Accuracy, and Performance |
title | Multipolar
Ewald Methods, 1: Theory, Accuracy, and
Performance |
title_full | Multipolar
Ewald Methods, 1: Theory, Accuracy, and
Performance |
title_fullStr | Multipolar
Ewald Methods, 1: Theory, Accuracy, and
Performance |
title_full_unstemmed | Multipolar
Ewald Methods, 1: Theory, Accuracy, and
Performance |
title_short | Multipolar
Ewald Methods, 1: Theory, Accuracy, and
Performance |
title_sort | multipolar
ewald methods, 1: theory, accuracy, and
performance |
url | https://www.ncbi.nlm.nih.gov/pmc/articles/PMC4325605/ https://www.ncbi.nlm.nih.gov/pubmed/25691829 http://dx.doi.org/10.1021/ct5007983 |
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