Optimized Basis Sets for Calculation of Electron Paramagnetic Resonance Hyperfine Coupling Constants: aug-cc-pVTZ-J for the 3d Atoms Sc–Zn

Hedegård, Erik D.; Kongsted, Jacob; Sauer, Stephan P. A.

doi:10.1021/ct200587k

Cited by 78 publications

(75 citation statements)

References 121 publications

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“…4 we show the effect of adding tight functions of different symmetries individually It has been shown previously that the addition of tight s-functions to standard correlation consistent basis sets is necessary to accurately calculate the HFS constants. 78,79 This is not Table 5 and Figure 1 contain the HFS constants of 137 BaF and 133 Cs, obtained at different levels of theory. In addition to the total HFS constants, the correlation contribution compared to the krDHF result is shown explicitly along with the deviation from experiment.…”

Section: Basis Setmentioning

confidence: 99%

Hyperfine Structure Constants on the Relativistic Coupled Cluster Level with Associated Uncertainties

et al. 2020

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Accurate predictions of hyperfine structure (HFS) constants are important in many areas of chemistry and physics, from the determination of nuclear electric and magnetic moments to benchmarking of new theoretical methods. We present a detailed investigation of the performance of the relativistic coupled cluster method for calculating HFS constants withing the finite-field scheme. The two selected test systems are 133 Cs and 137 BaF. Special attention has been paid to construct a theoretical uncertainty estimate based on investigations on basis set, electron correlation and relativistic effects. The largest contribution to the uncertainty estimate comes from higher order correlation contributions. Our conservative uncertainty estimate for the calculated HFS constants is ∼ 5.5%, while the actual deviation of our results from experimental values was < 1% in all cases.

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Section: Basis Setmentioning

confidence: 99%

Hyperfine Structure Constants on the Relativistic Coupled Cluster Level with Associated Uncertainties

et al. 2020

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“…The quality of the basis set is critical; in particular, the number of tight s-functions is important,w hichh as led to the development of specialized core-property basis sets for the lightert ransition metals. [3][4][5] It has been shown that aG aussian description of the nuclear charge(as an alternative to the standard non-relativistic point chargem odel)c an significantly improve the agreement with experimental results. [6][7][8] In density functional theory calculations of hyperfine couplings, the spin polarization of the core electrons should be properly described by the exchange-correlation functional.…”

Section: Introductionmentioning

confidence: 96%

Relativistic DFT Calculations of Hyperfine Coupling Constants in 5d Hexafluorido Complexes: [ReF₆]²⁻ and [IrF₆]²⁻

Haase

Repiský

Komorovský

et al. 2017

Chemistry A European J

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The performance of relativistic density functional theory (DFT) methods has been investigated for the calculation of the recently measured hyperfine coupling constants of hexafluorido complexes [ReF6]2− and [IrF6]2−. Three relativistic methods were employed at the DFT level of theory: the 2‐component zeroth‐order regular approximation (ZORA) method, in which the spin–orbit coupling was treated either variationally (EV ZORA) or as a perturbation (LR ZORA), and the 4‐component Dirac–Kohn–Sham (DKS) method. The dependence of the results on the basis set and the choice of exchange‐correlation functional was studied. Furthermore, the effect of varying the amount of Hartree–Fock exchange in the hybrid functionals was investigated. The LR ZORA and DKS methods combined with DFT led to very similar deviations (about 20 %) from the experimental values for the coupling constant of complex [ReF6]2− by using hybrid functionals. However, none of the methods were able to reproduce the large anisotropy of the hyperfine coupling tensor of complex [ReF6]2−. For [IrF6]2−, the EV ZORA and DKS methods reproduced the experimental tensor components with deviations of ≈10 and ≈5 % for the hybrid functionals, whereas the LR ZORA method predicted the coupling constant to be around one order of magnitude too large owing to the combination of large spin–orbit coupling and very low excitation energies.

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“…For Mn we used the aug-cc-pVTZ-J basis set developed by Sauer for the calculation of EPR parameters, which possesses a (25s17p10d3f2g)/[17s10p7d3f2g] contraction scheme and contains four tight s-, one tight p-, and one tight d-type function. 49 …”

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confidence: 99%

Mono-, Bi-, and Trinuclear Bis-Hydrated Mn²⁺ Complexes as Potential MRI Contrast Agents

Forgács

Regueiro‐Figueroa²,

Barriada³

et al. 2015

Inorg. Chem.

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We report a series of ligands containing pentadentate 6,6′-((methylazanediyl)bis(methylene))dipicolinic acid binding units that form mono- (H2dpama), di- (mX(H2dpama)2), and trinuclear (mX(H2dpama)3) complexes with Mn2+ containing two coordinated water molecules per metal ion, which results in pentagonal bipyramidal coordination around the metal ions. In contrast, the hexadentate ligand 6,6′-((ethane-1,2-diylbis(azanediyl))bis(methylene))dipicolinic acid (H2bcpe) forms a complex with distorted octahedral coordination around Mn2+ that lacks coordinated water molecules. The protonation constants of the ligands and the stability constants of the Mn2+, Cu2+, and Zn2+ complexes were determined using potentiometric and spectrophotometric titrations in 0.15 M NaCl. The pentadentate dpama2– ligand and the di- and trinucleating mX(dpama)24– and mX(dpama)36– ligands provide metal complexes with stabilities that are very similar to that of the complex with the hexadentate ligand bcpe2–, with log β101 values in the range 10.1–11.6. Cyclic voltammetry experiments on aqueous solutions of the [Mn(bcpe)] complex reveal a quasireversible system with a half-wave potential of +595 mV versus Ag/AgCl. However, [Mn(dpama)] did not suffer oxidation in the range 0.0–1.0 V, revealing a higher resistance toward oxidation. A detailed 1H NMRD and 17O NMR study provided insight into the parameters that govern the relaxivity for these systems. The exchange rate of the coordinated water molecules in [Mn(dpama)] is relatively fast, kex298 = (3.06 ± 0.16) × 108 s–1. The trinuclear [mX(Mn(dpama)(H2O)2)3] complex was found to bind human serum albumin with an association constant of 1286 ± 55 M–1 and a relaxivity of the adduct of 45.2 ± 0.6 mM–1 s–1 at 310 K and 20 MHz.

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Optimized Basis Sets for Calculation of Electron Paramagnetic Resonance Hyperfine Coupling Constants: aug-cc-pVTZ-J for the 3d Atoms Sc–Zn

Cited by 78 publications

References 121 publications

Hyperfine Structure Constants on the Relativistic Coupled Cluster Level with Associated Uncertainties

Hyperfine Structure Constants on the Relativistic Coupled Cluster Level with Associated Uncertainties

Relativistic DFT Calculations of Hyperfine Coupling Constants in 5d Hexafluorido Complexes: [ReF₆]²⁻ and [IrF₆]²⁻

Mono-, Bi-, and Trinuclear Bis-Hydrated Mn²⁺ Complexes as Potential MRI Contrast Agents

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Optimized Basis Sets for Calculation of Electron Paramagnetic Resonance Hyperfine Coupling Constants: aug-cc-pVTZ-J for the 3d Atoms Sc–Zn

Cited by 78 publications

References 121 publications

Hyperfine Structure Constants on the Relativistic Coupled Cluster Level with Associated Uncertainties

Hyperfine Structure Constants on the Relativistic Coupled Cluster Level with Associated Uncertainties

Relativistic DFT Calculations of Hyperfine Coupling Constants in 5d Hexafluorido Complexes: [ReF6]2− and [IrF6]2−

Mono-, Bi-, and Trinuclear Bis-Hydrated Mn2+ Complexes as Potential MRI Contrast Agents

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Relativistic DFT Calculations of Hyperfine Coupling Constants in 5d Hexafluorido Complexes: [ReF₆]²⁻ and [IrF₆]²⁻

Mono-, Bi-, and Trinuclear Bis-Hydrated Mn²⁺ Complexes as Potential MRI Contrast Agents