All-electron double zeta basis sets for the lanthanides: Application in atomic and molecular property calculations

Jorge, F.E.; Martins, L.S.C.; Franco, Mauro Lúcio

doi:10.1016/j.cplett.2015.11.013

Cited by 31 publications

(14 citation statements)

References 41 publications

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“…[6][7][8] All-electron Gaussian basis sets for lanthanides include third-order Douglas-Kroll (DK3) basis sets of Hirao and co-workers, 9,10 ANO-RCC basis sets, 11 SARC basis sets, 12,13 the segmented-contracted DKH basis set by Dolg, 14 Sapporo-DK-nZP, 15 cc-pVnZ basis sets, 6,16 and DZP and TZP basis sets by Jorge and co-workers. [17][18][19] The relativistic basis set family of Dyall and co-workers was developed for four-component Dirac-Hartree-Fock calculations. 20 More recently, the ANO-R basis sets 21 and Karlsruhe x2c basis sets 22,23 were optimized for the exact two-component (x2c) method.…”

Section: Introductionmentioning

confidence: 99%

Property-optimized Gaussian basis sets for lanthanides

Rappoport

2021

The Journal of Chemical Physics

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Property-optimized Gaussian basis sets of split-valence, triple-zeta and quadruplezeta valence quality are developed for the lanthanides Ce-Lu for use with small-core relativistic effective core potentials. They are constructed in a systematic fashion by augmenting def2 orbital basis sets with diffuse basis functions and minimizing negative static isotropic polarizabilities of lanthanide atoms with respect to basis set exponents within the unrestricted Hartree-Fock method. The basis set quality is assessed using a test set of 70 molecules containing the lanthanides in their common oxidation states and f electron occupations. 5d orbital occupation turns out to be the determining factor for the basis set convergence of polarizabilities in lanthanide atoms and the molecular test set. Therefore, two series of property-optimized basis sets are defined. The augmented def2-SVPD, def2-TZVPPD, and def2-QZVPPD basis sets balance the accuracy of polarizabilities across lanthanide oxidation states.The relative errors in atomic and molecular polarizability calculations are ≤ 8% for augmented split-valence basis sets, ≤ 2.5% for augmented triple-zeta valence basis sets, and ≤ 1% for augmented quadruple-zeta valence basis sets. In addition, extended def2-TZVPPDD and def2-QZVPPDD are provided for accurate calculations of lanthanide atoms and neutral clusters. The property-optimized basis sets developed in this work are shown to accurately reproduce electronic absorption spectra of a series of LnCp − 3 complexes (Cp = C 5 H 4 SiMe 3 , Ln = Ce-Nd, Sm) with timedependent density functional theory.

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Section: Introductionmentioning

confidence: 99%

Property-optimized Gaussian basis sets for lanthanides

Rappoport

2021

The Journal of Chemical Physics

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“…The routine set of experimental XRD data was used for the experimental-theoretical refinement. The one-point calculation of an isolated molecule of complex I was performed by the DFT method (B3LYP/DZP) [34] using the Gaussian 09 program [26]. Then the complex molecule was placed in the pseudocubic cell (а = 30 Å).…”

Section: Methodsmentioning

confidence: 99%

Application of the Molecular Invariom Model for the Study of Interactions Involving Fluorine Atoms in the {$${\text{Yb}}_{{\text{2}}}^{{{\text{II}}}}$$(μ2-OCH(CF3)2)3(μ3-OCH(CF3)2)2YbIII(OCH(CF3)2)2(THF)(Et2O)} Complex

et al. 2021

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The electron density distributions obtained by the quantum-chemical (density functional theory) calculations and molecular invariom model in the trimeric ytterbium complex with the hexafluoroisopropoxide ligands {$${\text{Yb}}_{{\text{2}}}^{{{\text{II}}}}$$(μ2-OR)3(μ3-OR)2YbIII(OR)2(THF)(Et2O)} (I) (where R is CH(CF3)2, and THF is tetrahydrofuran) are compared. The main topological characteristics of the electron density at the critical points (3, –1) corresponding to the interactions of the ytterbium atoms in the coordination sphere obtained using two studied approaches demonstrate excellent agreement. The maximum divergence between the density functional calculations and molecular invariom model is observed for the intramolecular interactions involving the fluorine atoms (F···F, F···H, and F···O) in the structure of complex I. Geometry optimization leads to a higher number of these interactions in the complex. The energy corresponding to these interactions also increases. However, the main topological characteristics for the F···X interactions (X = F, H, O), which can be localized in the framework of both methods, remain within the transferability index range. An analysis of the deformation electron density shows that the Fδ–···Fδ– interactions are determined by the correspondence of the region of electron density concentration on one of the fluorine atoms to the region of electron density depletion on the second fluorine atom regardless of the method of measuring the electron density distribution.

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“…The geometry optimizations of the isolated molecules 1 isol and 2 isol were performed by density functional theory using the B3LYP approach in the Gaussian 09 package . The all-electron DZP basis set was used for lanthanide atoms . The basis set 6-31G* was used for the organic fragments. − To obtain molecular invarioms of complexes 1 and 2 , single-point energy calculations (B3LYP/DZP for lanthanide atoms and 6-31G* for other atoms) were performed.…”

Section: Experimental Sectionmentioning

confidence: 99%

Unexpected Findings in a Simple Metathesis Reaction of Europium and Ytterbium Diiodides with Perfluorinated Mercaptobenzothiazolates of Alkali Metals

et al. 2020

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In the search for new f–d luminescent complexes of Eu(II) and Yb(II) the metathesis reactions of diiodides of these metals with perfluorinated 2-mercaptobenzothiazolates of alkali metals were studied. It has been found that the reactions of LnI2(THF)2 (Ln = Eu, Yb) with K(mbtF) (mbtF = perfluorinated 2-mercaptobenzothiazolate anion) in DME result in the formation of the nonluminescent complexes Ln(mbtF)2(DME)2 and precipitation of KI in high yields. Single-crystal X-ray diffraction analyses have shown that Eu(mbtF)2(DME)2 has a trans orientation of mbtF ligands, while in the Yb(mbtF)2(DME)2 molecule the ligands occupy cis positions. The DFT calculations and estimations with the invariom model revealed that the complexes have a flexible coordination sphere of Ln2+ ions and a relatively low energy of Ln–mbtF binding. The reactions of the same diiodides with the lithium complex Li(mbtF) are reversible and proceed through the formation of intermediate complexes of unknown structure which have been isolated as noncrystalline solids. The europium product (solid and in DME solution) upon UV excitation exhibited bright luminescence with λ 510 nm. Data from time-resolved photoluminescence (PL) spectroscopy indicated the existence in the intermediate substance of two Eu2+ emission centers with different coordinating environments. Treatment of the solid intermediate product with toluene led to its dissociation onto Ln(mbtF)2(DME)2 and [LiI(DME)] n . The back-replacement of toluene with DME gives again the solutions from which the starting LnI2 and Li(mbtF)(DME) were precipitated by slow evaporation of the solvent. The reversibility of the processes has been confirmed by the reaction of nonluminescent Eu(mbtF)2(DME)2 with LiI in DME medium, which resulted in the same luminescent solution which gave a mixture of EuI2(DME)3 and Li(mbtF).

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All-electron double zeta basis sets for the lanthanides: Application in atomic and molecular property calculations

Cited by 31 publications

References 41 publications

Property-optimized Gaussian basis sets for lanthanides

Property-optimized Gaussian basis sets for lanthanides

Application of the Molecular Invariom Model for the Study of Interactions Involving Fluorine Atoms in the {$${\text{Yb}}_{{\text{2}}}^{{{\text{II}}}}$$(μ2-OCH(CF3)2)3(μ3-OCH(CF3)2)2YbIII(OCH(CF3)2)2(THF)(Et2O)} Complex

Unexpected Findings in a Simple Metathesis Reaction of Europium and Ytterbium Diiodides with Perfluorinated Mercaptobenzothiazolates of Alkali Metals

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