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.

Spectroscopic properties and design of highly luminescent lanthanide coordination complexes

The theoretical description of charge distribution, and related properties, such as chemical reactivity descriptors of chemical compounds, has greatly benefited from the development of density functional theory (DFT) methods. Indeed, most concepts stemmed from DFT but, up to now, they have been used mostly within semiempirical MO methods, Hartree–Fock, or post-Hartree–Fock methods. During the last decade, however, DFT has enabled theoretical chemistry to predict accurately structures and energetics of clusters and molecules. Therefore, more attention should also now be paid to these reactivity descriptors determined directly from DFT calculations. In this work, chemical reactivity is explored in DFT through a functional Taylor expansion of energy that introduces various energy derivatives of chemical significance. This review summarizes their main features and examines the limitations of some indexes presently used for the characterization of reactivity. Also, several perspectives are given. © 1999 John Wiley & Sons, Inc. J Comput Chem 20: 129–154, 1999

Chemical reactivity indexes in density functional theory

Orbital interactions, electron delocalization and spin coupling in iron-sulfur clusters

Reactions of transition metal dihydrogen complexes

The Challenge of d and f electrons : theory and computation

Ligands on clusters - adsorbates on surfaces the chemistry of transition metal clusters surface science studies of molecular adsorbates on solid surfaces - a series of case studies concepts in heterogeneous catalysis electronic structure theory for transition metal systems - a survey selectivity in catalysis by metals and alloys metal-CO interactions - well-defined surfaces and supported particles linear semibridging carbonyls 5 the structure and bonding of the chromium cyclopentadienyl dicarbonyl dimer carbon dioxide organometallic chemistry - theoretical developments quantum chemical models of chemisorption on metal surfaces catalytic reactions of transition metal clusters and surfaces from ab initio theory reactivity and electronic structure of organometallic radicals density functional theory - principles and applications to metal-ligand interactions density functional model calculations for homogeneous and heterogenous catalysis a general energy decomposition scheme for the study of metal-ligand interactions in complexes clusters and solids physiochemical characterization of novel polymeric copper complexes with long-chain aliphatic diamines.

Metal-ligand interactions : from atoms, to clusters, to surfaces

Preface. List of Contributors. The Use of the Electron-Nucleus Hyperfine Interaction for Solution Structure Determination I. Bertini, et al. Modern Computational Approaches to Modeling Polynuclear Transition Metal Complexes D.A. Case, et al. Metal-Support Interaction in Catalysis B. Coq. Structure and Bonding of M(CO)5(H2O), M(CO)5(NH3) and M(CO)5(PH3) (M=Cr, Mo, W) G. Frenking, et al. Molecules on Clean and Modified Oxide Surfaces H.-J. Freund, et al. Foundations of Ab Initio Theory and Applications to Chemisorption and Bulk Properties Using the Cluster Model Approach From qualitative understanding to quantitative predictions F. Illas, et al. Spectroscopic and Electrochemical Studies of Coordination of Organic Molecules to Gold Single Crystal Surfaces J. Lipkowski, et al. Ionic Adsorption and Co-Adsorption at Single Crystal Electrodes J. Lipkowski, et al. Potential Energy Surfaces of Metal-Ligand Interactions Obtained Using Density Functional Theory T. Marino, et al. Band Theory: from Concepts to the LAPW Method K. Schwarz. Structures, Energetics, and Reactivity of Metal Clusters and Metal-Ligand Species in the Gas Phase. Review of Experimental Techniques and Future Directions B. Simard, et al. Theoretical Investigations of Silver Clusters and Silver-Ligand Systems S. Srinivas, et al. Ab Initio Investigations of Chemical Reactions Influenced by Transition Metal Catalysts H. Bogel, et al. Concepts in Double Groups - Do we Really Understand them for Practical Applications? A pedagogical study H.P. Fritzer. Fractal power Spectrum at Catalytic Oxidation of HCOOH over supported Pd Catalyst. Experiment and Theory M.K. Koleva, et al. Reactions of Mo Atoms and Cations with NO: ADensity Functional Study A.M. Koster, et al. In Situ Mossbauer Study of Mixed-Valency Catalysts for Methanol Oxidation I. Mitov, et al. Gas Separation by Adsorption: Molecular Simulation of Adsorption Properties of Zeolitic Materials P. Pullumbi, et al. Electronic Structure of Vanadia Systems: systematic Theoretical studies M. Witko, et al. Index. List of Participants.

Metal-ligand interactions in chemistry, physics and biology

Preface Density Functional Modeling of Ligand-Metal Interactions and Enzymatic Activities in Metalloenzymes: Peptide Bond Cleavage by Carboxypeptidase A YG Abashkin, et al Guided-Ion Beam Studies of Ionic Transition Metal Clusters and Complexes PB Armentrout Influence of Silys Ligands on the Reactivity of Heterobimetallic Complexes: Insertion and Migration Reactions P Braunstein, M Knorr Compounds of Post-Transition Elements of Group 12-14 Containing Fe(CO)4 and Related Iron Carbonyl Ligands F Calderoni, et al Ligand-Metal Surface Interactions: Synthesis, Structure and Reactivity ST Ceyer 2,2' Bipyrimidine: A Useful Tool in Designing Polynuclear Complexes of Controlled Nuclearity G de Munno, M Julve Influence of Particle Size on Metallic and Bimetallic Supported Catalysts: Hydrogenolysis of Hydrocarbons and Selective Hydrogenation of Nitro-Groups F Figueras, B Coq Quantum Mechanical Ab Initio Investigation of Metal-Ligand Interactions in Transition-Metal Carbonyl Complexes G Frenking, et al Clean and Modified Oxide Surfaces: Structure and Dynamics of Adsorbed Molecules H-J Freund Site and Size Effects on the Binding Energy of CO on Palladium Clusters: A Density Functional Treatment V Goncalves, C Mijoule Progress Towards a Molecular Surface Science: Dative Interactions in Chemistry at Metal Centres as Revealed by Spectroscopic, Kinetic and Dynamical Studies PA Hackett, et al Theoretical Dynamical Studies of Metal Clusters and Clusters-Ligand Systems J Jellinek The Role of Interelectronic Interaction in Transition Metal Oxide Catalysts N Neshev, Tz Mineva Coordinatively Unsaturated Pt and Pt-Re Clusters as Models for Surfaces and Bimetallic Catalysts RJ Puddephatt, J Xiao Molecular Adsorption of Diazirine on Palladium (110) Clusters Modelsusing the LCGTO-MCP-LSD Method A Rochefort, et al Metal-Ligand Interactions in Gas Phase and in Solution The Density Functional Point of View N Russo, et al Ab Initio Calculations of Electronic Surface States of Transition Metal Oxides and of the Superexchange Coupling in Oxo-Bridged Transition Metal Complexes V Staemmler Intermediate Neglect of Differential Overlap Calculations on the Electronic Spectra of Transition Metal Complexes MC Zerner Index

Dennis R. Salahub

Papers

The Challenge of d and f electrons : theory and computation

Metal-ligand interactions : from atoms, to clusters, to surfaces

Metal-ligand interactions in chemistry, physics and biology

Metal-ligand interactions : structure and reactivity

Metal-Ligand Interactions