Insight into the Electronic Structure of Formal Lanthanide(II) Complexes using Magnetic Circular Dichroism Spectroscopy

Fleischauer, Valerie E.; Ganguly, Gautam; Woen, David H.; Wolford, Nikki J.; Evans, William J.; Autschbach, Jochen; Neidig, Michael L.

doi:10.1021/acs.organomet.9b00315

“…As shown by the LnCp − 3 complexes (Ln = Ce-Nd, Sm), 5d occupation is not rare in low-valent lanthanide compounds. The response of the occupied d z 2 orbitals gives rise to novel optical [38][39][40]68,81 and magnetic 67,69,97,98 properties. Diffuse augmentation on lanthanide atoms is essential for accurate modeling of these properties.…”

Section: Discussionmentioning

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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“…As the example of LnCp − 3 complexes (Ln = Ce-Nd, Sm) shows, 5d occupation is far from rare in low-valent lanthanide compounds. The response of the occupied d z 2 orbitals gives rise to novel optical [38][39][40]66,81 and magnetic 65,67,97,98 properties. Diffuse augmentation on lanthanide atoms is essential for accurate modeling of these properties.…”

Section: Discussionmentioning

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

“…As shown by the LnCp − 3 complexes (Ln = Ce-Nd, Sm), 5d occupation is not rare in low-valent lanthanide compounds. The response of the occupied d z 2 orbitals gives rise to novel optical [38][39][40]68,81 and magnetic 67,69,97,98 properties. Diffuse augmentation on lanthanide atoms is essential for accurate modeling of these properties.…”

Section: Discussionmentioning

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.

show abstract

Insight into the Electronic Structure of Formal Lanthanide(II) Complexes using Magnetic Circular Dichroism Spectroscopy

Cited by 22 publications

References 43 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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