A diagonalization-free optimization algorithm for solving Kohn-Sham equations of closed-shell molecules
© 2020 Wiley Periodicals LLC.
| Veröffentlicht in: | Journal of computational chemistry. - 1984. - 42(2021), 7 vom: 15. März, Seite 492-504 |
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| Format: | Online-Aufsatz |
| Sprache: | English |
| Veröffentlicht: |
2021
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| Zugriff auf das übergeordnete Werk: | Journal of computational chemistry |
| Schlagworte: | Journal Article Grassmann manifold Kohn-Sham equations constrained optimization local minimizer tangent set projection |
| Zusammenfassung: | © 2020 Wiley Periodicals LLC. A local optimization algorithm for solving the Kohn-Sham equations is presented. It is based on a direct minimization of the energy functional under the equality constraints representing the Grassmann Manifold. The algorithm does not require an eigendecomposition, which may be advantageous in large-scale computations. It is optimized to reduce the number of Kohn-Sham matrix evaluations to one per iteration to be competitive with standard self-consistent field (SCF) approach accelerated by direct inversion of the iterative subspace (DIIS). Numerical experiments include a comparison of the algorithm with DIIS. A high reliability of the algorithm is observed in configurations where SCF iterations fail to converge or find a wrong solution corresponding to a stationary point different from the global minimum. The local optimization algorithm itself does not guarantee that the found minimum is global. However, a randomization of the initial approximation shows a convergence to the right minimum in the vast majority of cases |
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| Beschreibung: | Date Revised 29.01.2021 published: Print-Electronic Citation Status PubMed-not-MEDLINE |
| ISSN: | 1096-987X |
| DOI: | 10.1002/jcc.26472 |