All-electron basis sets augmented with diffuse functions for He, Ca, Sr, Ba, and lanthanides: application in calculations of atomic and molecular properties

Ferreira, I. B.; Campos, C.T.; Jorge, F.E.

doi:10.1007/s00894-020-04365-w

“…[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%

“…15 Jorge and co-workers developed augmented basis sets from energy optimizations of atomic anions. 18,19 The latter two approaches tend to produce extensive augmentation and small diffuse basis set exponents, which impact the efficiency of integraldirect methods and can cause numerical stability problems.…”

Section: Introductionmentioning

confidence: 99%

Property-optimized Gaussian basis sets for lanthanides

Rappoport

¹

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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“…[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

¹

2021

Preprint

0

View full text Add to dashboard Cite

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.

show abstract

“…[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

¹

2021

Preprint

0

View full text Add to dashboard Cite

Property-optimized Gaussian basis sets of split-valence, triple-zeta and quadruple-zeta 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' = C5H4SiMe3, Ln = Ce–Nd, Sm) with time-dependent density functional theory.

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All-electron basis sets augmented with diffuse functions for He, Ca, Sr, Ba, and lanthanides: application in calculations of atomic and molecular properties

Cited by 9 publications

References 60 publications

Property-optimized Gaussian basis sets for lanthanides

Property-optimized Gaussian basis sets for lanthanides

Property-Optimized Gaussian Basis Sets for Lanthanides

Property-Optimized Gaussian Basis Sets for Lanthanides

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