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  Efficient implementation of the analytic second derivatives of Hartree–Fock and hybrid DFT energies: a detailed analysis of different approximations

Bykov, D., Petrenko, T., Izsák, R., Kossmann, S., Becker, U., Valeev, E., et al. (2015). Efficient implementation of the analytic second derivatives of Hartree–Fock and hybrid DFT energies: a detailed analysis of different approximations. Molecular Physics, 113(13-14), 1961-1977. doi:10.1080/00268976.2015.1025114.

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 Creators:
Bykov, Dmytro1, Author           
Petrenko, Taras1, Author           
Izsák, Róbert1, Author           
Kossmann, Simone1, Author           
Becker, Ute1, Author           
Valeev, Edward2, Author
Neese, Frank1, Author           
Affiliations:
1Research Department Neese, Max Planck Institute for Chemical Energy Conversion, Max Planck Society, ou_3023886              
2Department of Chemistry, Virginia Tech, Blacksburg, Virginia USA, ou_persistent22              

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Free keywords: molecular Hessian; Hartree-Fock; Density Functional Theory; COSX
 Abstract: In this paper, various implementations of the analytic Hartree–Fock and hybrid density functional energy second derivatives are studied. An approximation-free four-centre implementation is presented, and its accuracy is rigorously analysed in terms of self-consistent field (SCF), coupled-perturbed SCF (CP-SCF) convergence and prescreening criteria. The CP-SCF residual norm convergence threshold turns out to be the most important of these. Final choices of convergence thresholds are made such that an accuracy of the vibrational frequencies of better than 5 cm−1 compared to the numerical noise-free results is obtained, even for the highly sensitive low frequencies (<100–200 cm−1). The effects of the choice of numerical grid for density functional exchange–correlation integrations are studied and various weight derivative schemes are analysed in detail. In the second step of the work, approximations are introduced in order to speed up the computation without compromising its accuracy. To this end, the accuracy and efficiency of the resolution of identity approximation for the Coulomb terms and the semi-numerical chain of spheres approximation to the exchange terms are carefully analysed. It is shown that the largest performance improvements are realised if either Hartree–Fock exchange is absent (pure density functionals) and otherwise, if the exchange terms in the CP-SCF step of the calculation are approximated by the COSX method in conjunction with a small integration grid. Default values for all the involved truncation parameters are suggested. For vancomycine (176 atoms and 3593 basis functions), the RIJCOSX Hessian calculation with the B3LYP functional and the def2-TZVP basis set takes ∼3 days using 16 Intel® Xeon® 2.60GHz processors with the COSX algorithm having a net parallelisation scaling of 11.9 which is at least ∼20 times faster than the calculation without the RIJCOSX approximation.

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Language(s): eng - English
 Dates: 2014-12-082015-03-252015-07-18
 Publication Status: Published in print
 Pages: 17
 Publishing info: -
 Table of Contents: -
 Rev. Type: Peer
 Identifiers: DOI: 10.1080/00268976.2015.1025114
 Degree: -

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Title: Molecular Physics
  Abbreviation : Mol. Phys.
Source Genre: Journal
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Publ. Info: London : Taylor & Francis
Pages: - Volume / Issue: 113 (13-14) Sequence Number: - Start / End Page: 1961 - 1977 Identifier: ISSN: 0026-8976
CoNE: https://pure.mpg.de/cone/journals/resource/954925264211