We introduce in this work a new approach to the identification of localized electronic groups in atomic and molecular systems. Our approach is based on local behavior of the Hartree–Fock parallel‐spin pair probability and is completely independent of unitary orbital transformations. We derive a simple ‘‘electron localization function’’ (ELF) which easily reveals atomic shell structure and core, binding, and lone electron pairs in simple molecular systems as well.

A Simple Measure of Electron Localization in Atomic and Molecular-Systems

I. Introduction: Conceptual vs Fundamental andComputational Aspects of DFT1793II. Fundamental and Computational Aspects of DFT 1795A. The Basics of DFT: The Hohenberg−KohnTheorems1795B. DFT as a Tool for Calculating Atomic andMolecular Properties: The Kohn−ShamEquations1796C. Electronic Chemical Potential andElectronegativity: Bridging Computational andConceptual DFT1797III. DFT-Based Concepts and Principles 1798A. General Scheme: Nalewajski’s ChargeSensitivity Analysis1798B. Concepts and Their Calculation 18001. Electronegativity and the ElectronicChemical Potential18002. Global Hardness and Softness 18023. The Electronic Fukui Function, LocalSoftness, and Softness Kernel18074. Local Hardness and Hardness Kernel 18135. The Molecular Shape FunctionsSimilarity 18146. The Nuclear Fukui Function and ItsDerivatives18167. Spin-Polarized Generalizations 18198. Solvent Effects 18209. Time Evolution of Reactivity Indices 1821C. Principles 18221. Sanderson’s Electronegativity EqualizationPrinciple18222. Pearson’s Hard and Soft Acids andBases Principle18253. The Maximum Hardness Principle 1829IV. Applications 1833A. Atoms and Functional Groups 1833B. Molecular Properties 18381. Dipole Moment, Hardness, Softness, andRelated Properties18382. Conformation 18403. Aromaticity 1840C. Reactivity 18421. Introduction 18422. Comparison of Intramolecular ReactivitySequences18443. Comparison of Intermolecular ReactivitySequences18494. Excited States 1857D. Clusters and Catalysis 1858V. Conclusions 1860VI. Glossary of Most Important Symbols andAcronyms1860VII. Acknowledgments 1861VIII. Note Added in Proof 1862IX. References 1865

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Conceptual density functional theory.

Free Radical Lipid Peroxidation: Mechanisms and Analysis

The primary producs formed from the autoxidation of lipids can be understood based upon a mechanism that involves five different reaction types. These reactions are: reaction of a carbon radical and molecular oxygen, atom transfer of a hydrogen from substrate to the chain carrying peroxyl, fragmentation of the chain carrying peroxyl to give oxygen and a carbon radical, rearrangement of the peroxyl, and cyclization of the peroxyl. The mechanisms of these primary reaction steps has been the focus of extensive research over the past fifty years, and the current level of understanding of these transformations is the subject of this review.

Mechanisms of free radical oxidation of unsaturated lipids

Chemical bonding in transition metal carbonyl clusters: complementary analysis of theoretical and experimental electron densities

It is shown that the form of the Laplacian of the charge density provides a more complete resolution of the shell structure of atoms than the radial density function. The complete shell structure is resolved for s‐block and most p‐block atoms, but only the inner shells are resolved in the d‐block elements. The shell structures revealed by the Laplacian of the charge density and the radial density function parallel one another where direct comparison is possible.

The shell structure of atoms and the Laplacian of the charge density

A systematic analysis of electron correlation effects in model S N 2 reactions shows large differences between the structures optimized at the Hartree-Fock (HF) and second-order Moller-Plesset (MP2) levels, but the relative energies critical to an understanding of gas-phase S N 2 reactions are essentially unaffected by the effect of electron correlation on the optimized structures

An ab initio study of model SN2 reactions with inclusion of electron correlation effects through second-order Moeller-Plesset perturbation calculations.

Transition-state electronic structures in SN2 reactions

Geometries for the molecules in the series C 2 H n F 6-n (n=0-6) and for the radicals produced by homolytic cleavage of the C-C and C-H bonds have been optimized at the MP2/6-31G(d,p) level. A few calculations at the MP4/6-311G-(d,p)//MP2/6-31G(d,p) level have been included to show that higher order correlation effects do not change the observed trends. The preferred conformations of the substituted ethyl radicals indicate that the gauche effect operates in the radicals as well as in the parent molecules

Zheng Shi

Papers

The shell structure of atoms and the Laplacian of the charge density

An ab initio study of model SN2 reactions with inclusion of electron correlation effects through second-order Moeller-Plesset perturbation calculations.

Transition-state electronic structures in SN2 reactions

Effects of electron correlation on the series C2HnF6-n (n = 0-6) : geometries, total energies, and C-C and C-H bond dissociation energies

The Laplacian of the charge density as a probe of reaction paths and reactivity: a comparison of SN2 reactions at carbon and silicon