Eleonora Echegaray

Reaction electronic flux: a new concept to get insights into reaction mechanisms. Study of model symmetric nucleophilic substitutions.

The present work is focused on studying chlorine and fluorine identity SN2 substitutions on a methyl center, within the framework of the newly introduced reaction electronic flux J(xi), that allows one to identify charge transfer and polarization mechanisms that take place along the reaction coordinate. The main results concern the discovery of different charge transfer mechanism, despite both reactions have the same energetic pattern with simultaneous bond breaking and formation. It turns out that the chlorine substitution is mainly driven by polarization effects and characterized by through bond interactions while intermolecular charge transfer dominates the fluorine exchange reaction, that is characterized by through space interactions.

Pointing the way to the products? Comparison of the stress tensor and the second-derivative tensor of the electron density

The eigenvectors of the electronic stress tensor can be used to identify where new bond paths form in a chemical reaction. In cases where the eigenvectors of the stress tensor are not available, the gradient-expansion-approximation suggests using the eigenvalues of the second derivative tensor of the electron density instead; this approximation can be made quantitatively accurate by scaling and shifting the second-derivative tensor, but it has a weaker physical basis and less predictive power for chemical reactivity than the stress tensor. These tools provide an extension of the quantum theory of atoms and molecules from the characterization of molecular electronic structure to the prediction of chemical reactivity.

Relationships between the third-order reactivity indicators in chemical density-functional theory

Relationships between third-order reactivity indicators in the closed system [N, v(r)], open system [mu, v(r)], and density [rho(r)] pictures are derived. Our method of derivation unifies and extends known results. Among the relationships is a link between the third-order response of the energy to changes in the density and the quadratic response of the density to changes in external potential. This provides a link between hyperpolarizability and the systems sensitivity to changes in electron density. The dual descriptor is a unifying feature of many of the formulas we derive.

In pursuit of negative Fukui functions: examples where the highest occupied molecular orbital fails to dominate the chemical reactivity

AbstractIn our quest to explore molecules with chemically significant regions where the Fukui function is negative, we explored reactions where the frontier orbital that indicates the sites for electrophilic attack is not the highest occupied molecular orbital. The highest occupied molecular orbital (HOMO) controls the location of the regions where the Fukui function is negative, supporting the postulate that negative values of the Fukui function are associated with orbital relaxation effects and nodal surfaces of the frontier orbitals. Significant negative values for the condensed Fukui function, however, were not observed.n FigureThe −10−5isosurface of

In pursuit of negative Fukui functions: molecules with very small band gaps

{f^{-}}left( mathbf{r} right)

Negative Condensed-to-Atom Fukui Functions: A Signature of Oxidation-Induced Reduction of Functional Groups

(opaque silver surface) traces the nodal regions of the HOMO (translucent colored lobes, with different colors for different phases) of the phenoxide anion

The reaction electronic flux in chemical reactions

The mechanism of a simple S(N)2 reaction, viz; OH(-) + CH(3)F = CH(3)OH + F(-) has been studied within the framework of reaction force and reaction electronic flux. We have computationally investigated three different types of reaction mechanisms with two different types of transition states, leading to two different products. The electronic transfer contribution of the reaction electronic flux was found to play a crucial role in this reaction. Natural bond order analysis and dual descriptor provide additional support for elucidating the mechanism of this reaction.

The mechanics of charge-shift bonds: A perspective from the electronic stress tensor

AbstractA justification for the likely presence of negative Fukui functions in molecules with small band gaps is given, and a computational study performed to check whether molecules with small band gaps have negative Fukui functions to a chemically significant extent is reported. While regions with negative Fukui functions were observed, significantly negative values for the atom-condensed Fukui functions were not observed.n FigureThe silver surface encapsulates the negative regions of the Fukui function, which occur in nodal regions of the HOMO (translucent colored lobes, with different colors for different phases) for this phenalenyl biradical.