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Pulay forces from localized orbitals optimized in situ using a psinc basis set
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Ruiz-Serrano, Alvaro, Hine, Nicholas and Skylaris, Chris-Kriton (2012) Pulay forces from localized orbitals optimized in situ using a psinc basis set. Journal of Chemical Physics, 136 (23). 234101 . doi:10.1063/1.4728026 ISSN 0021-9606.
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Official URL: http://dx.doi.org/10.1063/1.4728026
Abstract
In situoptimization of a set of localized orbitals with respect to a systematically improvable basis set independent of the position of the atoms, such as psinc functions, would theoretically eliminate the correction due to Pulay forces from the total ionic forces. We demonstrate that for strict localization constraints, especially with small localization regions, there can be non-negligible Pulay forces that must be calculated as a correction to the Hellmann-Feynman forces in the ground state. Geometry optimization calculations, which rely heavily upon accurate evaluation of the total ionic forces, show much better convergence when Pulay forces are included. The more conventional case, where the local orbitals remain fixed to pseudo-atomic orbital multiple-ζ basis sets, also benefits from this implementation. We have validated the method on several test cases, including a DNA fragment with 1045 atoms.
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 | ||||||||
Journal or Publication Title: | Journal of Chemical Physics | ||||||||
Publisher: | American Institute of Physics | ||||||||
ISSN: | 0021-9606 | ||||||||
Official Date: | June 2012 | ||||||||
Dates: |
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Volume: | 136 | ||||||||
Number: | 23 | ||||||||
Article Number: | 234101 | ||||||||
DOI: | 10.1063/1.4728026 | ||||||||
Status: | Peer Reviewed | ||||||||
Publication Status: | Published | ||||||||
Access rights to Published version: | Restricted or Subscription Access | ||||||||
Date of first compliant deposit: | 30 March 2016 | ||||||||
Date of first compliant Open Access: | 5 April 2016 | ||||||||
Funder: | Engineering and Physical Sciences Research Council (EPSRC), Royal Society (Great Britain) | ||||||||
Grant number: | EP/G05567X/1 (EPSRC), EP/G05567X/1 (EPSRC) |
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