The role of induced current density in Steroelectronic effects: Perlin effect

Hernández-Lima, Joseelyne; Barquera‐Lozada, José Enrique; Cuevas, Gabriel; Cortés‐Guzmán, Fernando

doi:10.1002/jcc.23965

Cited by 15 publications

(16 citation statements)

References 32 publications

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“…Hernández‐Lima et al used J (1) ( r ) and its atomic partition to understand the Perlin effect in cyclic organic molecules, Figure . The Perlin effect is the differing behavior of geminal hydrogen atoms with regard to their chemical shift, where δ ax < δ eq ( δ ax > δ eq for the reverse Perlin effect), where δ ax and δ eq are the axial and equatorial chemical shifts, respectively.…”

Section: Applications Of Qtaimmentioning

confidence: 99%

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Latin American contributions to quantum chemical topology

García‐Revilla

Cortés‐Guzmán

Rocha‐Rinza

et al. 2018

Int J of Quantum Chemistry

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We survey the contributions from Latin American theoretical chemists to the field of quantum chemical topology (QCT) over nearly the last 30 years with emphasis on the developments and applications of the quantum theory of atoms in molecules (QTAIM). Applications of QCT in the fields of excited states, electron delocalization, chemical bond, aromaticity, conformational analysis, spectroscopic properties, and chemical reactivity are presented. We also consider the coupling of QTAIM with time‐dependent density functional theory, the virial theorem in the Kohn‐Sham method and the inclusion of electron dynamical correlation in the interacting quantum atoms method using coupled cluster and multi‐configurational densities. Additionally, we describe the development of efficient algorithms for the calculation of topological properties derived from the electron density. This review is aimed not only at providing an account of the contributions to QCT in Latin America but also at stimulating guides for further progress in the field.

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Section: Applications Of Qtaimmentioning

confidence: 99%

“…Induced current density by a magnetic field in the H ax –C–H eq plane and perpendicular to the C–H ax (A, C) and C–H eq of cyclohexane (A, B) and 1,3‐dithiane (C, D) bonds …”

Section: Applications Of Qtaimmentioning

confidence: 99%

Latin American contributions to quantum chemical topology

García‐Revilla

Cortés‐Guzmán

Rocha‐Rinza

et al. 2018

Int J of Quantum Chemistry

Self Cite

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“…The magnetically induced current density ( J ( r )) is the quantum mechanical observable that is directly connected to these electronic flows. Studying the topology of J ( r ) is important to understand NMR chemical shifts or the magnetic susceptibility of a molecule . It can also be used to study the electron delocalization in bonds and molecules .…”

Section: Introductionmentioning

confidence: 99%

“…The strength and tropicity of J ( r ) are also useful to explain the shielding constants of nuclei close to a specific circulation. The chemical shift of nuclei above or below a paratropic/diatropic current would be shifted downfield (deshielded)/upfield (shielded) in an NMR spectrum, respectively …”

Section: Introductionmentioning

confidence: 99%

Vorticity: Simplifying the analysis of the current density

Barquera‐Lozada

2019

J Comput Chem

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The induced current density (J(r)) provides useful information about the electronic structure of molecules under a magnetic field (B). However, the analysis of its topology is cumbersome because of its vectorial nature. We show that its tropicity (direction of rotation) and its strength can be compressed in the triple product B ⋅ ∇ × J(r) (tpJ(r)) that is a scalar field. The topology of tpJ(r) has clear similarities to the Laplacian of the electron density. Additionally, the topology of aromatic and antiaromatic compounds is notoriously different. The vorticity of J(r) is helpful to define the circulation of the current density, C, that contrary to other methods, can be easily defined for individual rings in polycyclic molecules. This allows tpJ(r) to clearly reproduce the Clar's structure of polycyclic aromatic hydrocarbons. © 2019 Wiley Periodicals, Inc.

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“…For example, in a previous study we showed that for a series of cyclohexanes in which 1,3 positions were interchanged by a heteroatom and present Perlin effect, there are at least two directions of B that correlate with the observed trends. Both B directions are necessary to explain the chemical shifts . Another example is fullerenes, in which the electron delocalization occurs in a three‐dimensional space.…”

Section: Introductionmentioning

confidence: 99%

The vorticity of the current density tensor and 3D‐aromaticity

Barquera‐Lozada

2018

Int J of Quantum Chemistry

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The induced current density (J(r)) vector field has been extensively used as a criterion of aromaticity and electron delocalization. However, the selection of the direction of the perturbing magnetic field (B) is arbitrary and in the case of three‐dimensional electron delocalization/aromaticity the selection could be ambiguous. The J(r) has also recently received some criticism as an aromaticity index. We propose the Trace of the Vorticity of the Current Density tensor (TVCD) scalar field as a more suitable quantity for the evaluation of electron delocalization of three‐dimensional systems. It does not depend on the orientation of B and contrary to other related scalar fields like the anisotropy of the induced current density, it does not lose the information of the direction of the currents. We show that not only the currents parallel to the molecular plane are important in the evaluation of the aromaticity, as is largely believed, but also the perpendicular ones, which information is included in the TVCD. The TVCD is very useful to study planar and 3D delocalized molecules (eg, fullerenes). Moreover, the integration of the TVCD over an internal surface of the 3D‐cages serves as index for 3D‐aromaticity.

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The role of induced current density in Steroelectronic effects: Perlin effect

Cited by 15 publications

References 32 publications

Latin American contributions to quantum chemical topology

Latin American contributions to quantum chemical topology

Vorticity: Simplifying the analysis of the current density

The vorticity of the current density tensor and 3D‐aromaticity

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