Revisiting the definition of local hardness and hardness kernel

文献情報

出版日 2017-03-31

DOI 10.1039/C7CP00691H

インパクトファクター 3.676

著者

Carlos A. Polanco-Ramírez, Javier Carmona-Espíndola, José L. Gázquez, Paul W. Ayers

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要旨

An analysis of the hardness kernel and local hardness is performed to propose new definitions for these quantities that follow a similar pattern to the one that characterizes the quantities associated with softness, that is, we have derived new definitions for which the integral of the hardness kernel over the whole space of one of the variables leads to local hardness, and the integral of local hardness over the whole space leads to global hardness. A basic aspect of the present approach is that global hardness keeps its identity as the second derivative of energy with respect to the number of electrons. Local hardness thus obtained depends on the first and second derivatives of energy and electron density with respect to the number of electrons. When these derivatives are approximated by a smooth quadratic interpolation of energy, the expression for local hardness reduces to the one intuitively proposed by Meneses, Tiznado, Contreras and Fuentealba. However, when one combines the first directional derivatives with smooth second derivatives one finds additional terms that allow one to differentiate local hardness for electrophilic attack from the one for nucleophilic attack. Numerical results related to electrophilic attacks on substituted pyridines, substituted benzenes and substituted ethenes are presented to show the overall performance of the new definition.

掲載誌

Physical Chemistry Chemical Physics

CiteScore: 5.5

自己引用率: 10.3%

年間論文数: 3036

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