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An efficient orbital transformation method for electronic structure calculations


VandeVondle, J; Hutter, J (2003). An efficient orbital transformation method for electronic structure calculations. Journal of Chemical Physics, 118(10):4365-4369.

Abstract

An efficient method for optimizing single-determinant wave functions of medium and large systems is presented. It is based on a minimization of the energy functional using a new set of variables to perform orbital transformations. With this method convergence of the wave function is guaranteed. Preconditioners with different computational cost and efficiency have been constructed. Depending on the preconditioner, the method needs a number of iterations that is very similar to the established diagonalization-DIIS approach, in cases where the latter converges well. Diagonalization of the Kohn-Sham matrix can be avoided and the sparsity of the overlap and Kohn-Sham matrix can be exploited. If sparsity is taken into account, the method scales as O(MN2), where M is the total number of basis functions and N is the number of occupied orbitals. The relative performance of the method is optimal for large systems that are described with high quality basis sets, and for which the density matrices are not yet sparse. We present a benchmark calculation on a DNA crystal containing 2x12 base pairs, solvent and counter ions (2388 atoms), using a TZV(2d,2p) basis (38 688 basis functions) and conclude that the electronic structure of systems of this size can now be studied routinely.

An efficient method for optimizing single-determinant wave functions of medium and large systems is presented. It is based on a minimization of the energy functional using a new set of variables to perform orbital transformations. With this method convergence of the wave function is guaranteed. Preconditioners with different computational cost and efficiency have been constructed. Depending on the preconditioner, the method needs a number of iterations that is very similar to the established diagonalization-DIIS approach, in cases where the latter converges well. Diagonalization of the Kohn-Sham matrix can be avoided and the sparsity of the overlap and Kohn-Sham matrix can be exploited. If sparsity is taken into account, the method scales as O(MN2), where M is the total number of basis functions and N is the number of occupied orbitals. The relative performance of the method is optimal for large systems that are described with high quality basis sets, and for which the density matrices are not yet sparse. We present a benchmark calculation on a DNA crystal containing 2x12 base pairs, solvent and counter ions (2388 atoms), using a TZV(2d,2p) basis (38 688 basis functions) and conclude that the electronic structure of systems of this size can now be studied routinely.

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Additional indexing

Item Type:Journal Article, refereed, original work
Communities & Collections:07 Faculty of Science > Department of Chemistry
Dewey Decimal Classification:540 Chemistry
Language:English
Date:2003
Deposited On:27 Mar 2009 08:19
Last Modified:01 Jun 2016 13:01
Publisher:American Institute of Physics
ISSN:0021-9606
Additional Information:Copyright 2003 American Institute of Physics. This article may be downloaded for personal use only. Any other use requires prior permission of the author and the American Institute of Physics. The following article appeared in J. Chem. Phys. 118, 4365 (2003); DOI:10.1063/1.1543154 and may be found at http://dx.doi.org/10.1063/1.1543154
Free access at:Publisher DOI. An embargo period may apply.
Publisher DOI:10.1063/1.1543154
Permanent URL: http://doi.org/10.5167/uzh-3190

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