Assessment of higher-order spin–orbit effects on electronic g-tensors of d 1 transition-metal complexes by relativistic two- and four-component methods
| Autor: | Veronika Hrobáriková, Martin Kaupp, Peter Hrobárik, Stanislav Komorovský, Michal Repiský |
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| Rok vydání: | 2011 |
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| Zdroj: | Theoretical Chemistry Accounts. 129:715-725 |
| ISSN: | 1432-2234 1432-881X |
| DOI: | 10.1007/s00214-011-0951-7 |
| Popis: | The electronic g-tensors of a series of V, Cr, Mo, W, Tc, and Re d1 transition-metal complexes have been studied systematically by density functional theory (DFT) methods. The comparison between one-component second-order perturbation theory calculations with two- and four-component first-order perturbation calculations has allowed an assessment of the importance of higher-order spin-orbit contributions. Using an efficient matrix Dirac–Kohn–Sham implementation with relativistic kinetic balance basis sets, it has been possible for the first time to apply four-component DFT also to g-tensors of larger models for biological vanadium, molybdenum, and tungsten metal sites. Higher-order spin–orbit effects are generally crucial for an accurate determination of the g-tensors in such complexes, in many cases more important than the choice of non-hybrid or hybrid density functional. A systematic scaling analysis of the spin–orbit integrals shows that second-order spin–orbit effects may be of the same size as the leading first-order effects and thus alter the computed g-tensors fundamentally, in particular for the 5d species. In the latter case, even third-order effects may be non-negligible. |
| Databáze: | OpenAIRE |
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