Relativistic quantum chemistry involving heavy atoms

Santis, Matteo De; Belapassi, Leonardo; Tarantelli, Francesco; Storchi, Loriano

doi:10.1007/s12210-018-0706-7

Cited by 3 publications

(2 citation statements)

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“…The sets are formed so that to an auxiliary function of a given angular momentum all the functions of smaller angular momentum are associated. Consequently, due to the variational nature of the density fitting procedure implemented, a fitting basis set of increased accuracy can be generated by simply up-shifting the angular momentum in the basis set definition . For Cu and Ag, we achieved a fitting basis set of higher accuracy (referred to as A2) simply by up-shifting of two units the angular momentum of all the DeMon Coulomb Fitting definitions.…”

Section: Methods and Computational Detailsmentioning

confidence: 99%

“…Consequently, due to the variational nature of the density fitting procedure implemented, a fitting basis set of increased accuracy can be generated by simply up-shifting the angular momentum in the basis set definition. 90 For Cu and Ag, we achieved a fitting basis set of higher accuracy (referred to as A2) simply by up-shifting of two units the angular momentum of all the DeMon Coulomb Fitting definitions. For the sake of clarity we give the dimension of the C-atom (or equivalently N-atom) auxiliary basis sets, which is (7s,7p,7d,3f,3g).…”

Section: ■ Conclusionmentioning

confidence: 99%

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The Chemical Bond and s–d Hybridization in Coinage Metal(I) Cyanides

et al. 2019

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We present a four-component relativistic density functional theory study of the chemical bond and s-d hybridization in the group-11 cyanides MCN (M = Cu, Ag, Au). The analysis is carried out within the charge-displacement/natural orbital for chemical valence (CD-NOCV) scheme, which allows us to single out meaningful contributions to the total charge rearrangement that arises upon bond formation and to quantify the components of the Dewar-Chatt-Duncanson bonding model (the ligand-tometal donation and metal-to-ligand back-donation). The M-CN bond is characterized by a large donation from the cyanide ion to the metal cation and by two small backdonation components from the metal towards the cyanide anion. The case of gold cyanide elucidates the peculiar role of the relativistic eects in determining the characteristics of the AuC bond with respect to the copper and silver homologues. In AuCN, the donation and back-donation components are signicantly enhanced and the spinorbit coupling, removing the degeneracy of the 5d atomic orbitals, induces a substantial split in the back-donation components. A simple spatial analysis of the NOCV-pair density, related to the ligand-to-metal donation component, allows us to quantify, with unprecedented accuracy, the charge rearrangement due to the s-d hybridization occurring at the metal site. The s-d hybridization plays a key role in determining the shape and size of the metal: it removes electron density from the bond axis and induces a signicant attening at the metal site in trans position to the ligand. The s-d hybridization is present in all noble metal complexes, inuencing the bond distances, and its eect is enhanced for Au, which is consistent with the preference of gold to form linear complexes. A comparative investigation of simple complexes [AuL] +/0 of Au + with dierent ligands (L=F − , N-Heterocyclic Carbene, CO, PH 3) shows that the s-d hybridization mechanism is also inuenced by the nature of the ligand.

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Section: Methods and Computational Detailsmentioning

confidence: 99%

Section: ■ Conclusionmentioning

confidence: 99%

The Chemical Bond and s–d Hybridization in Coinage Metal(I) Cyanides

et al. 2019

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Relativistic Atomic Structure

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2023

Springer Handbooks

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BERTHA: Implementation of a four-component Dirac–Kohn–Sham relativistic framework

Belpassi

Santis

Quiney

et al. 2020

The Journal of Chemical Physics

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In this paper, we present and review the most recent computational advances in the BERTHA code. BERTHA can be regarded as the state of the art in fully relativistic four-component Dirac–Kohn–Sham (DKS) software. Thanks to the implementation of various parallelization and memory open-ended distribution schemes in combination with efficient “density fitting” algorithms, it greatly reduces the computational burden of four-component DKS calculations. We also report the newly developed OpenMP version of the code, that, together with the berthmod Python module, provides a significant leap forward in terms of usability and applicability of the BERTHA software. Some applications of the recently developed natural orbitals for chemical valence/charge displacement bonding analysis and the real-time time dependent DKS implementation are also reported.

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Relativistic quantum chemistry involving heavy atoms

Cited by 3 publications

References 52 publications

The Chemical Bond and s–d Hybridization in Coinage Metal(I) Cyanides

The Chemical Bond and s–d Hybridization in Coinage Metal(I) Cyanides

Relativistic Atomic Structure

BERTHA: Implementation of a four-component Dirac–Kohn–Sham relativistic framework

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