2024-03-29T07:54:37Zhttps://repositori.uji.es/oai/requestoai:repositori.uji.es:10234/1710392022-02-02T18:27:54Zcom_10234_7013com_10234_9col_10234_8638
Repositori UJI
author
de la LANDE, Aurélien
author
Moliner, Vicent
author
Parisel, Olivier
2017-12-15T12:17:50Z
2017-12-15T12:17:50Z
2007-07
DE LA LANDE, Aurélien; MOLINER, Vicent; PARISEL, Olivier. Singlet-triplet gaps in large multireference systems: Spin-flip-driven alternatives for bioinorganic modeling. The Journal of chemical physics, 2007, vol. 126, no 3, p. 01B613.
http://hdl.handle.net/10234/171039
https://doi.org/10.1063/1.2423010
The proper description of low-spin states of open-shell systems, which are commonly encountered in the field of bioinorganic chemistry, rigorously requires using multireference ab initio methodologies. Such approaches are unfortunately very CPU-time consuming as dynamic correlation effects also have to be taken into account. The broken-symmetry unrestricted (spin-polarized) density functional theory (DFT) technique has been widely employed up to now to bypass that drawback, but despite a number of relative successes in the determination of singlet-triplet gaps, this framework cannot be considered as entirely satisfactory. In this contribution, we investigate some alternative ways relying on the spin-flip time-dependent DFT approach [Y. Shao et al. J. Chem. Phys. 118, 4807 (2003)]. Taking a few well-documented copper-dioxygen adducts as examples, we show that spin-flip (SF)-DFT computed singlet-triplet gaps compare very favorably to either experimental results or large-scale CASMP2 computations. Moreover, it is shown that this approach can be used to optimize geometries at a DFT level including some multireference effects. Finally, a clear-cut added value of the SF-DFT computations is drawn: if pure ab initio data are required, then the electronic excitations revealed by SF-DFT can be considered in designing dramatically reduced zeroth-order variational spaces to be used in subsequent multireference configuration interaction or multireference perturbation treatments.
eng
© 2007 American Institute of Physics.
bioinorganic chemistry
bioinorganic modeling
singlet-triplet gaps
correlation methods
mathematical models
perturbation techniques
probability density function
Singlet-triplet gaps in large multireference systems: spin-flip-driven alternatives for bioinorganic modelling
info:eu-repo/semantics/article
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