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An improved algorithm for the normalized elimination of the small-component method

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Abstract

A new algorithm for the iterative solution of the normalized elimination of the small component (NESC) method is presented that is less costly than previous algorithms and that is based on (1) solving the NESC equations for the uncontracted rather than contracted basis (“First-Diagonalize-then-Contract”), (2) a new iterative procedure for obtaining the NESC Hamiltonian (“iterative TU algorithm”), (3) the renormalization scheme connected to the picture change, and (4) a finite nucleus model with a Gaussian charge distribution. The accuracy of NESC energies, which match those of 4-component Dirac calculations, is demonstrated. Test calculations with CCSD(T), DFT, and large basis sets including high angular momentum basis functions (f,g,h,i) are presented to prove the general applicability of the new NESC algorithm. Comparison with other algorithms of solving the NESC equations are shortly discussed and time savings are presented.

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Acknowledgments

This work was financially supported by the National Science Foundation, Grant CHE 071893. We thank SMU for providing computational resources. MF is grateful to SMU for the invitation as a visiting professor.

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Authors and Affiliations

  1. Department of Chemistry, Southern Methodist University, 3215 Daniel Ave, Dallas, TX, 75275-0314, USA

    Wenli Zou & Dieter Cremer

  2. University of Groningen, 9747 AG, Groningen, The Netherlands

    Michael Filatov

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  1. Wenli Zou
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  2. Michael Filatov
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  3. Dieter Cremer
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Correspondence to Dieter Cremer.

Additional information

Dedicated to Professor Akira Imamura on the occasion of his 77th birthday and published as part of the Imamura Festschrift Issue.

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Zou, W., Filatov, M. & Cremer, D. An improved algorithm for the normalized elimination of the small-component method. Theor Chem Acc 130, 633–644 (2011). https://doi.org/10.1007/s00214-011-1007-8

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