How does relativity affect magnetically induced currents?

Berger, Raphael J. F.; Repiský, Michal; Komorovský, Stanislav

doi:10.1039/c5cc05732a

Cited by 24 publications

(49 citation statements)

References 22 publications

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“… at four‐component relativistic level, which had allowed the extraction of the SO contributions to these current loops. Current plots showed diatropic current loops (see also ref. ) around the hydride in HAu and small SO‐induced localized paratropic current loops for HHgH, consistent with shielding 1 H σ SO for HAu and a deshielding one for HHgH (cf.…”

Section: Resultsmentioning

confidence: 99%

Insights into trans‐Ligand and Spin‐Orbit Effects on Electronic Structure and Ligand NMR Shifts in Transition‐Metal Complexes

Greif

Hrobárik

Kaupp

2017

Chemistry A European J

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Surprisingly general effects of trans ligands L on the ligand NMR shifts in third-row transition-metal complexes have been found by quasi-relativistic computations, encompassing 5d , 5d , and to some extent even 5d situations. Closer analysis, with emphasis on H shieldings in a series of linear HAu L complexes, reveals a dominance of spin-orbit (SO) effects, which can change sign from appreciably shielding for weak trans ligands to appreciably deshielding for ligands with strong trans influence. This may be traced back to increasing destabilization of a σ-type MO at scalar relativistic level, which translates into very different σ-/π-mixing if SO coupling is included. For the strongest trans ligands, the σ-MO may move above the highest occupied π-type MOs, thereby dramatically reducing strongly shielding contributions from predominantly π-type spinors. The effects of SO-mixing are in turn related to angular momentum admixture from atomic spinors at the metal center. These SO-induced trends hold for other nuclei and may also be used to qualitatively predict shifts in unknown complexes.

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Section: Resultsmentioning

confidence: 99%

Insights into trans‐Ligand and Spin‐Orbit Effects on Electronic Structure and Ligand NMR Shifts in Transition‐Metal Complexes

Greif

Hrobárik

Kaupp

2017

Chemistry A European J

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“…Conversely, relativistic effects on interatomic currents have been reported for the molecules AuH and HgH 2 . [20] In general, only a few authors have investigated interatomic currents; the studies of hydrogen bonded systems via MICDs appear as the most relevant ones. [21,22] The literature on other attempts to extract chemical information from MICDs is scarce.…”

Section: Introductionmentioning

confidence: 99%

Information on Gas‐Phase Diatomic Molecules from Magnetically Induced Current Densities

Alvarez‐Thon

Mammino

2017

J Comput Chem

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Magnetically induced current densities are different for different types of chemical bonds, and may help highlight some of their characteristics and stress their main differences. The present work considers magnetically induced current densities in the bonds of diatomic molecules bonded by covalent bonds as well as the gas phase molecules of 1:1 ionic compounds, comparing the current strength values and visualizing current density maps. The results show clear-cut differences for the different types of bonds (non-polar covalent, polar covalent, and ionic), and can also be related to the extent of the covalent or ionic character of a bond. For ionic compounds, the results also show relevant differences depending on the charges of the ions and on their electron configuration (including significant effects from the presence of d electrons in the outer shell of the ions). The article presents and analyses the results in detail. It is concluded that the magnetically induced current densities contribute to the description and interpretation of chemical bonding in diatomic molecules.

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“…In this work, the influence of the SO coupling on MICDs is only significant for the

{Bi}_{5}^{-}

and

{Mc}_{5}^{-}

clusters. Other authors have also reported important changes, on magnetic properties, upon inclusion of the SO coupling in their calculations …”

Section: Resultsmentioning

confidence: 89%

“…The SO coupling has been reported to affect magnetic and aromatic properties on molecules containing heavy atoms . For example, in the MICD study of the hexahalogenated benzenes

{normalC}_{6} {normalX}_{6}

(

X = H, F, Cl, Br, I, At

), the SO effect on the RCS of

{normalC}_{6} {normalI}_{6}

turned out to be significant, but in

{normalC}_{6} {At}_{6}

the neglect of the SO coupling is dramatic, quenching the RCS by about 50% .…”

Section: Introductionmentioning

confidence: 99%

Spin–orbit effects on magnetically induced current densities in the () clusters

Alvarez‐Thon

Inostroza-Pino

2018

J Comput Chem

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This study reports the spin-orbit effects on the aromaticity of the N5-, P5-, As5-, Sb5-, Bi5-, and Mc5- anionic clusters via the magnetically induced current-density method. All-electron density functional theory (DFT) calculations were carried out using the four-component Dirac-Coulomb (DC) hamiltonian, including scalar and spin-orbit relativistic effects. The magnetic index of aromaticity was calculated by numerical integration over the current flow between two atoms in the pentagonal ring. These values were compared to the spin-free values (spin-orbit coupling switched off), in order to assess the spin-orbit effect on aromaticity. It was found that in the heavy anions, Bi5- and Mc5-, there is a significant influence of the spin-orbit coupling. © 2018 Wiley Periodicals, Inc.

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How does relativity affect magnetically induced currents?

Cited by 24 publications

References 22 publications

Insights into trans‐Ligand and Spin‐Orbit Effects on Electronic Structure and Ligand NMR Shifts in Transition‐Metal Complexes

Insights into trans‐Ligand and Spin‐Orbit Effects on Electronic Structure and Ligand NMR Shifts in Transition‐Metal Complexes

Information on Gas‐Phase Diatomic Molecules from Magnetically Induced Current Densities

Spin–orbit effects on magnetically induced current densities in the () clusters

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