Revisiting electroaccepting and electrodonating powers: proposals for local electrophilicity and local nucleophilicity descriptors

Literature Information

Publication Date 2014-10-03
DOI 10.1039/C4CP03167A
Impact Factor 3.676
Authors

Christophe Morell, Alberto Vela, Frédéric Guégan, Henry Chermette


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Abstract

The electrophilicity index, μ2/2η, where μ is the chemical potential and η is the hardness, has been defined by Parr, Von Szentpaly, and Liu (J. Am. Chem. Soc., 1999, 121, 1922) as the lowering in energy of an electronic system during a process in which the chemical potential of the system raises from μ to zero, accepting −μ/η electrons. In this work, it is shown that the electrophilicity index is also a rational choice for measuring nucleophilicity. Indeed, within the grand canonical ensemble, when the chemical potential of a system increases from μ to zero, the system gives away μ/η electrons. During the process, the variation of the grand potential is μ2/2η. Additionally, through the use of a second order Taylor series expansion of the density as a function of the number of electrons, at constant external potential, which depends on the Fukui function and the dual descriptor, the local electrophilicity is defined as the actual variation of the electron density when the system acquires −μ/η electrons, while the local nucleophilicity is similarly defined for the case when the system loses μ/η electrons.

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Physical Chemistry Chemical Physics

Physical Chemistry Chemical Physics
CiteScore: 5.5
Self-citation Rate: 10.3%
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Physical Chemistry Chemical Physics (PCCP) is an international journal co-owned by 19 physical chemistry and physics societies from around the world. This journal publishes original, cutting-edge research in physical chemistry, chemical physics and biophysical chemistry. To be suitable for publication in PCCP, articles must include significant innovation and/or insight into physical chemistry; this is the most important criterion that reviewers and Editors will judge against when evaluating submissions. The journal has a broad scope and welcomes contributions spanning experiment, theory, computation and data science. Topical coverage includes spectroscopy, dynamics, kinetics, statistical mechanics, thermodynamics, electrochemistry, catalysis, surface science, quantum mechanics, quantum computing and machine learning. Interdisciplinary research areas such as polymers and soft matter, materials, nanoscience, energy, surfaces/interfaces, and biophysical chemistry are welcomed if they demonstrate significant innovation and/or insight into physical chemistry. Joined experimental/theoretical studies are particularly appreciated when complementary and based on up-to-date approaches.

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