Proposal of a simple and effective local reactivity descriptor through a topological analysis of an orbital‐weighted fukui function

Abstract

The prediction of reactivity is one of the long-standing objectives of chemistry, contributing to enforce the link between theory and experiment. In particular, the regioselectivity of aromatic molecules has motivated the proposal of different reactivity descriptors based on foundational theories, like Frontier Molecular Orbital (FMO) theory and density functional theory, to predict and rationalize such regioselectivity. This article examines cases where reactivity descriptors, based on FMO theories, are known to have failed, specifically on electrophilic aromatic substitution reactions, through a simple but effective new reactivity model: the Orbital-weighted Fukui function ( fw-(r)) and its topological analysis. Interestingly, this descriptor proves to be effective in adequately predicting regioselectivities where other approximations failed. © 2017 Wiley Periodicals, Inc.

A Fukui function‐guided genetic algorithm. Assessment on structural prediction of Sin (n = 12–20) clusters

“…[63] The topological analysis of f 6r ð Þ can be easily performed using a pipeline (TAFF) published elsewhere. [64] For the exploration of the PES using GEGA procedure, the PBE0 [60] /SDALL [65] level was used. Subsequently, the lowest energy structures (<30 kcal mol 21 ) were reoptimized and harmonic frequencies were calculated at PBE0/Def2TZVP [66] level (the relatives reported in this paper include zero point energy corrections).…”

Interpreting Aromaticity and Antiaromaticity through Bifurcation Analysis of the Induced Magnetic Field

“…In theoretical chemistry, this has already been done in the pioneer works of Bader, which originated the Quantum Theory of Atoms in Molecules (QTAIM). Later, this topological analysis has been applied to interpret the Electron Localization Function,, and more recently to the Fukui function ,. Regarding this current work, we are particularly interested in the bifurcation analysis applied to one magnetic property, the induced magnetic field ( .…”

“…Aromaticity is one of the most commonly cited concepts in chemical literature due to its broad application to rationalize the stability of a great variety of molecules nowadays . Although aromaticity is not an experimentally measurable quantity, many indices from different criteria have been proposed to characterize and quantify it (see references above for further details). The magnetic criteria is based on the fact that aromatic compounds sustain an induced ring current density in the presence of both a normal –to the molecular plane‐ and a uniform external magnetic field In turn, this current induces a characteristic magnetic field ( which is different to the external magnetic field .…”

“…Later, this topological analysis has been applied to interpret the Electron Localization Function, [2,5] and more recently to the Fukui function. [1,6] Regarding this current work, we are particularly interested in the bifurcation analysis applied to one magnetic property, the induced magnetic field (B ind Þ. This analysis is applied to a series of molecular rings, and consists in identifying the (3, À 1) critical points of the scalar function B ind r ð Þ that connect a number of irreducible domains forming a global reducible ring-shaped domain.…”

Estudio teórico de cupratos de litio como posibles materiales catódicos para baterías

“…Se han realizado esfuerzos para ir más allá de esta aproximación [85,89,91], sin embargo, en este trabajo se aplicó la ecuación 6-6 para estimar la s(r), donde ∆µ se fijó mediante la condición:…”