Calculation of transition matrix elements by nonsingular orbital transformations
| Autor: | Mojmír Kývala |
|---|---|
| Rok vydání: | 2008 |
| Předmět: |
Basis (linear algebra)
Chemistry Molecular orbital theory Condensed Matter Physics Atomic and Molecular Physics and Optics Slater-type orbital law.invention Delocalized electron Invertible matrix law Computational chemistry Quantum mechanics Slater determinant Molecular orbital Physical and Theoretical Chemistry Wave function |
| Zdroj: | International Journal of Quantum Chemistry. 109:1200-1227 |
| ISSN: | 0020-7608 |
| DOI: | 10.1002/qua.21935 |
| Popis: | A general strategy is described for the evaluation of transition matrix elements between pairs of full class CI wave functions built up from mutually nonorthogonal molecular orbitals. A new method is proposed for the counter-transformation of the linear expansion coefficients of a full CI wave function under a nonsingular transformation of the molecular-orbital basis. The method, which consists in a straightforward application of the Cauchy–Binet formula to the definition of a Slater determinant, is shown to be simple and suitable for efficient implementation on current high-performance computers. The new method appears mainly beneficial to the calculation of miscellaneous transition matrix elements among individually optimized CASSCF states and to the re-evaluation of the CASCI expansion coefficients in Slater-determinant bases formed from arbitrarily rotated (e.g., localized or, conversely, delocalized) active molecular orbitals. © 2008 Wiley Periodicals, Inc. Int J Quantum Chem, 2009 |
| Databáze: | OpenAIRE |
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