Multiplets of free d- and f-metal ions: A systematic DFT study

Borel, Alain; Daul, Claude

doi:10.1016/j.theochem.2005.09.023

Cited by 8 publications

(7 citation statements)

References 31 publications

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“…section S1) we find that the metal complex in its crystalline form has a high-spin (HS) ground state with S=5/2. This is as expected from ligand-field theory since exchange interactions at the metal core are large enough [24,25] to overcome the nearly octahedral energy splitting Δ oct [26]. Thus it would be natural to assign this high-spin ground state with N=5 d-electrons on the Mn-atom to region (1), which makes region (2) a 6-particle state, with an extra electron fluctuating between the Mn d-orbitals and a ligand state.…”

supporting

confidence: 72%

Electrical Manipulation of Spin States in a Single Electrostatically Gated Transition-Metal Complex

et al. 2009

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We demonstrate an electrically controlled high-spin (S = 5/2) to low-spin (S = 1/2) transition in a three-terminal device incorporating a single Mn(2+) ion coordinated by two terpyridine ligands. By adjusting the gate-voltage we reduce the terpyridine moiety and thereby strengthen the ligand-field on the Mn-atom. Adding a single electron thus stabilizes the low-spin configuration and the corresponding sequential tunnelling current is suppressed by spin-blockade. From low-temperature inelastic cotunneling spectroscopy, we infer the magnetic excitation spectrum of the molecule and uncover also a strongly gate-dependent singlet-triplet splitting on the low-spin side. The measured bias-spectroscopy is shown to be consistent with an exact diagonalization of the Mn-complex, and an interpretation of the data is given in terms of a simplified effective model.

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confidence: 72%

Electrical Manipulation of Spin States in a Single Electrostatically Gated Transition-Metal Complex

et al. 2009

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“…[21][22][23][24] Herein, we are just giving a brief summary of the general methodology. The LFDFT model, which includes two-open-shells f-and d-electrons presented here, is an extension of the previously published models being successfully applied to the physical properties of transition metals [25][26][27] or lanthanide complexes. 25,[28][29][30] In LFDFT, the central Pr 3+ ion is subjected to a perturbation due to the surrounding ligands.…”

Section: Methodsmentioning

confidence: 99%

“…We developed the concept of a multideterminental DFT, based on the association of ligand field theory and DFT, forming the acronyms LFDFT. 23,24 The analysis of the single open-shell transition metal d-electrons [25][26][27] or the lanthanide f-electrons 25,[28][29][30] is well established and currently practiced, while the consideration of the two-open-shells, i.e. f-and d-electrons, is a challenge solved in the present work.…”

Section: Introductionmentioning

confidence: 98%

Ligand field density functional theory calculation of the 4f2 → 4f15d1 transitions in the quantum cutter Cs2KYF6:Pr3+

Ramanantoanina

Urland

Cimpoesu³

et al. 2013

Phys. Chem. Chem. Phys.

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Herein we present a Ligand Field Density Functional Theory (LFDFT) based methodology for the analysis of the 4f n -4f nÀ1 5d 1 transitions in rare earth compounds and apply it for the characterization of the show that the occupation of the three undistorted sites allows a quantum-cutting process. However size effects due to the difference between the ionic radii of Pr 3+ and K + as well as Cs + lead to the distortion of the K + -and the Cs + -site, which finally exclude these sites for quantum-cutting. A detailed discussion about the origin of this distortion is also described.

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“…32,[39][40][41][42][43][44] However, there is unfortunately no general way to a priori estimate this monodeterminantal character except, maybe, by comparison to known very closely related species, an hazardous procedure, however. The only way to get an estimate of the single-reference character is to perform dedicated CI, multiconfiguration self-consistent field ͑MC-SCF͒, or complete active space self-consistent field ͑CASSCF͒ calculations.…”

Section: 3538mentioning

confidence: 99%

Singlet-triplet gaps in large multireference systems: Spin-flip-driven alternatives for bioinorganic modeling

Lande

Moliner²,

Parisel³

2007

The Journal of Chemical Physics

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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.

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Multiplets of free d- and f-metal ions: A systematic DFT study

Abstract: In this work we apply in a systematic way our multi-determinantal model to calculate the fine structure of the whole atomic multiplet manifold. The key feature of this approach is the explicit treatment of near degeneracy correlation using ad hoc Configuration Interaction (CI) within the

Cited by 8 publications

References 31 publications

Electrical Manipulation of Spin States in a Single Electrostatically Gated Transition-Metal Complex

Electrical Manipulation of Spin States in a Single Electrostatically Gated Transition-Metal Complex

Ligand field density functional theory calculation of the 4f2 → 4f15d1 transitions in the quantum cutter Cs2KYF6:Pr3+

Singlet-triplet gaps in large multireference systems: Spin-flip-driven alternatives for bioinorganic modeling

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