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  An improved chain of spheres for exchange algorithm

Helmich-Paris, B., de Souza, B., Neese, F., & Izsák, R. (2021). An improved chain of spheres for exchange algorithm. The Journal of Chemical Physics, 155(10): 104109. doi:10.1063/5.0058766.

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 Creators:
Helmich-Paris, Benjamin1, Author           
de Souza, Bernardo2, Author           
Neese, Frank3, Author           
Izsák, Róbert4, 5, Author           
Affiliations:
1Research Group Helmich-Paris, Max-Planck-Institut für Kohlenforschung, Max Planck Society, ou_2541712              
2FAccTs GmbH, Rolandstrasse 67, 50677 Köln, Germany, ou_persistent22              
3Research Department Neese, Max-Planck-Institut für Kohlenforschung, Max Planck Society, ou_2541710              
4Research Group Izsák, Max-Planck-Institut für Kohlenforschung, Max Planck Society, ou_2541707              
5Middlebury College, Chemistry and Biochemistry, McCardell Bicentennial Hall, Middlebury, Vermont 05753, USA, ou_persistent22              

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 Abstract: In the present work, we describe a more accurate and efficient variant of the chain-of-spheres algorithm (COSX) for exchange matrix computations. Higher accuracy for the numerical integration is obtained with new grids that were developed using global optimization techniques. With our new default grids, the average absolute energy errors are much lower than 0.1 kcal/mol, which is desirable to achieve “chemical accuracy.” Although the size of the new grids is increased by roughly a factor of 2.5, the excellent efficiency of the original COSX implementation is still further improved in most cases. The evaluation of the analytic electrostatic potential integrals was significantly accelerated by a new implementation of rolled-out versions of the Dupuis–Rys–King and Head-Gordon–Pople algorithms. Compared to our earlier implementation, a twofold speedup is obtained for the frequently used triple-ζ basis sets, while up to a 16-fold speedup is observed for quadruple-ζ basis sets. These large gains are a consequence of both the more efficient integral evaluation and the intermediate exchange matrix computation in a partially contracted basis when generally contracted shells occur. With our new RIJCOSX implementation, we facilitate accurate self-consistent field (SCF) binding energy calculations on a large supra-molecular complex composed of 320 atoms. The binding-energy errors with respect to the fully analytic results are well below 0.1 kcal/mol for the cc-pV(T/Q)Z basis sets and even smaller than for RIJ with fully analytic exchange. At the same time, our RIJCOSX SCF calculation even with the cc-pVQZ basis and the finest grid is 21 times faster than the fully analytic calculation.

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Language(s): eng - English
 Dates: 2021-06-022021-08-232021-09-132021-09-14
 Publication Status: Published in print
 Pages: 14
 Publishing info: -
 Table of Contents: -
 Rev. Type: Peer
 Identifiers: DOI: 10.1063/5.0058766
 Degree: -

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Title: The Journal of Chemical Physics
  Abbreviation : J. Chem. Phys.
Source Genre: Journal
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Publ. Info: Woodbury, N.Y. : American Institute of Physics
Pages: - Volume / Issue: 155 (10) Sequence Number: 104109 Start / End Page: - Identifier: ISSN: 0021-9606
CoNE: https://pure.mpg.de/cone/journals/resource/954922836226