An efficient algorithm for energy gradients and orbital optimization in valence bond theory
An efficient algorithm for energy gradients in valence bond theory with nonorthogonal orbitals is presented. A general Hartree-Fock-like expression for the Hamiltonian matrix element between valence bond (VB) determinants is derived by introducing a transition density matrix. Analytical expressions...
| Veröffentlicht in: | Journal of computational chemistry. - 1984. - 30(2009), 3 vom: 15. Feb., Seite 399-406 |
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| 1. Verfasser: | |
| Weitere Verfasser: | , , |
| Format: | Online-Aufsatz |
| Sprache: | English |
| Veröffentlicht: |
2009
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| Zugriff auf das übergeordnete Werk: | Journal of computational chemistry |
| Schlagworte: | Journal Article Research Support, Non-U.S. Gov't |
| Zusammenfassung: | An efficient algorithm for energy gradients in valence bond theory with nonorthogonal orbitals is presented. A general Hartree-Fock-like expression for the Hamiltonian matrix element between valence bond (VB) determinants is derived by introducing a transition density matrix. Analytical expressions for the energy gradients with respect to the orbital coefficients are obtained explicitly, whose scaling for computational cost is m(4), where m is the number of basis functions, and is thus approximately the same as in HF method. Compared with other existing approaches, the present algorithm has lower scaling, and thus is much more efficient. Furthermore, the expression for the energy gradient with respect to the nuclear coordinates is also presented, and it provides an effective algorithm for the geometry optimization and the evaluation of various molecular properties in VB theory. Test applications show that our new algorithm runs faster than other methods |
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| Beschreibung: | Date Completed 23.02.2009 Date Revised 28.03.2012 published: Print CommentIn: J Comput Chem. 2012 Mar 30;33(8):911-3; discussion 914-5. - PMID 22278948 Citation Status MEDLINE |
| ISSN: | 1096-987X |
| DOI: | 10.1002/jcc.21065 |