Relativistic effects on the aromaticity of the halogenated benzenes: C 6 X 6 , X = H, F, Cl, Br, I, At

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.

“…In

{normalN}_{5}^{-}

, the current‐density pathways are similar to those found in benzene, reported by other authors . Essentially, in the molecular plane of

{normalN}_{5}^{-}

, there are paratropic (counterclockwise) currents inside the ring of nitrogen atoms and diatropic (clockwise) currents flowing outside the ring.…”

Section: Resultssupporting

confidence: 83%

“…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%

{Bi}_{5}^{-}

and

{Mc}_{5}^{-}

clusters, can be realized when compared to the net RCS of benzene (∼

12 nA / T

) …”

Section: Resultsmentioning

confidence: 93%

“…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% . In another study of the

{normalM}_{4}^{2 -}

(M = B, Al, Ga, In, Tl)

series of clusters, only the

{Tl}_{4}^{2 -}

cluster presents a significant influence of the SO coupling on the RCS …”

Section: Introductionmentioning

confidence: 99%

See 2 more Smart Citations

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

Inostroza-Pino

2018

J Comput Chem

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“…[10][11][12] This technique has been applied to benzene and other planar structures where the current is sustained by a ring of chemically bonded atoms. [1,11,[13][14][15][16][17] Under the action of an applied external field, current flows through all chemical bonds. As Sundholm et al write in their excellent review, [8] "When a molecule is exposed to an external magnetic field its electrons are forced to move around parts of the molecule or around the entire molecule, giving rise to a magnetically induced current density."…”

Section: Introductionmentioning

confidence: 99%

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

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.

An investigation of aromaticity in hydroxybenzenes based on the study of magnetically induced current density

Mammino

2017

Int J Quantum Chem

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Hydroxybenzenes are derivatives of benzene in which one or more H atoms are replaced by OH groups. This work considers the effect of such replacement on the aromaticity of the ring, by assessing the aromaticity through the values and patterns of the magnetically induced current density. The results show that aromaticity is quenched and the quenching depends on the number and positions of the substituting OH groups. The isosurfaces of the magnitude of the current density also highlight connections between the donor and acceptor atoms forming an intramolecular hydrogen bond. K E Y W O R D S aromaticity, current density, current strength, diatropic, paratropic Int J Quantum Chem. 2017;117:e25382.