Theoretical modeling of two-step spin-crossover transitions in FeII dinuclear systems
A computational methodology to model the spin-transition in the dinuclear iron(II) systems [Fe(bt)(NCX)2]2(μ-bpym) and [Fe(pypzH)(NCX)]2(μ-pypz)2 (X = S, Se or BH3) is presented. Using the hybrid meta-GGA exchange-correlation functional TPSSh, accurate values for the thermochemical quantities associ...
| Autores: | , |
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| Tipo de recurso: | artículo |
| Estado: | Versión aceptada para publicación |
| Fecha de publicación: | 2015 |
| País: | España |
| Institución: | Varias* (Consorci de Biblioteques Universitáries de Catalunya, Centre de Serveis Científics i Acadèmics de Catalunya) |
| Repositorio: | Recercat. Dipósit de la Recerca de Catalunya |
| OAI Identifier: | oai:recercat.cat:2445/154554 |
| Acceso en línea: | https://hdl.handle.net/2445/154554 |
| Access Level: | acceso abierto |
| Palabra clave: | Teoria del funcional de densitat Spin (Física nuclear) Density functionals Nuclear spin |
| Sumario: | A computational methodology to model the spin-transition in the dinuclear iron(II) systems [Fe(bt)(NCX)2]2(μ-bpym) and [Fe(pypzH)(NCX)]2(μ-pypz)2 (X = S, Se or BH3) is presented. Using the hybrid meta-GGA exchange-correlation functional TPSSh, accurate values for the thermochemical quantities associated with the different spin-states can be computed, and subsequently used to calculate the corresponding transition temperatures. This results also allow for the correct modeling of the spin-crossover curve, in agreement with the two-step or single-step nature experimentally reported for the transition. Our results indicate that the presence or absence of a two-step transition is mostly dominated by electronic effects and cooperativity between binding pockets plays a minor role. Insight in the electronic structure effects that enhance or suppress this behavior and its origins can be outlined from direct analysis of the relevant d-based molecular orbitals, which allows for a quantitative computational prediction to screen for new dinuclear systems with selected properties. |
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