Chemical Bond

Gernot Frenking studied chemistry at the Technical University Aachen (Germany). He then became a research atudent in the group of Prof. Kenichi Fukui in Kyoto (Japan) and completed his PhD and his habilitation at Technical University Berlin (Germany). He was then a visiting scientist at the University of California, Berkeley (USA) and a staff scientist at SRI International in Menlo Park, California (USA). Since 1990 he is Professor for Computational Chemistry at the Philipps-Universitat Marburg. Sason Shaik is a graduate of the University of Washington (USA), where he also obtained his PhD. After a postdoctoral year at Cornell University, he became Lecturer at Ben-Gurion University of the Negev (Israel), where he became Professor in 1988. In 1992 he moved to The Hebrew University where he is Professor and the Director of the Lise Meitner-Minerva Center for Computational Quantum Chemistry.

• Preface CHEMICAL BONDING OF MAIN-GROUP ELEMENTSIntroduction and DefinitionsThe Lack of Radial Nodes of the 2p Shell Accounts for Most of the Peculiarities of the Chemistry of the 2p-ElementsThe Role of the Outer d-Orbitals in BondingSecondary Periodicities: Incomplete-Screening and Relativistic Effects"Honorary d-Elements": the Peculiarities of Structure and Bonding of the Heavy Group 2 ElementsConcluding Remarks MULTIPLE BONDING OF HEAVY MAIN-GROUP ATOMSIntroductionBonding Analysis of Diatomic Molecules E2 (E = N -Bi)Comparative Bonding Analysis of N2 and P2 with N4 and P4Bonding Analysis of the Tetrylynes HEEH (E = C -Pb)Explaining the Different Structures of the Tetrylynes HEEH (E = C -Pb)Energy Decomposition Analysis of the Tetrylynes HEEH (E = C -Pb)Conclusion THE ROLE OF RECOUPLED PAIR BONDING IN HYPERVALENT MOLECULESIntroductionMultireference Wavefunction Treatment of BondingLow-Lying States of SF and OFLow-Lying States of SF2 and OF2 (and Beyond)Comparison to Other ModelsConcluding Remarks DONOR-ACCEPTOR COMPLEXES OF MAIN-GROUP ELEMENTSIntroductionSingle-Center Complexes EL2Two-Center Complexes E2L2Summary and Conclusion ELECTRON-COUNTING RULES IN CLUSTER BONDING -POLYHEDRAL BORANES, ELEMENTAL BORON, AND BORON-RICH SOLIDSIntroductionWade's RuleLocalized Bonding Schemes for Bonding in Polyhedral Boranes4n + 2 Interstitial Electron Rule and Ring-Cap Orbital Overlap CompatibilityCapping PrincipleElectronic Requirement of Condensed Polyhedral Boranes - mno RuleFactors Affecting the Stability of Condensed Polyhedral ClustersHypoelectronic MetallaboranesElectronic Structure of Elemental Boron and Boron-Rich Metal Borides -Application of Electron-Counting RulesConclusion BOUND TRIPLET PAIRS IN THE HIGHEST SPIN STATES OF MONOVALENT METAL CLUSTERSIntroductionCan Triplet Pairs Be Bonded?Origins of NPFM Bonding in n+1Lin ClustersGeneralization of NPFM Bonding in n+1Lin ClustersNPFM Bonding in Coinage Metal ClustersValence Bond Modeling of the Bonding in NPFM Clusters of the Coinage MetalsNPFM Bonding: Resonating Bound Triplet PairsConcluding Remarks: Bound Triplet PairsAppendix CHEMICAL BONDING IN TRANSITION METAL COMPOUNDSIntroductionValence Orbitals and Hybridization in Electron-Sharing Bonds of Transition MetalsCarbonyl Complexes TM(CO)6q (TMq = Hf2-, Ta-, W, Re+, Os2+, Ir3+)Phosphane Complexes (CO)5TM-PR3 and N-Heterocyclic Carbene Complexes (CO)5TM-NHC (TM = Cr, Mo, W)Ethylene and Acetylene Complexes (CO)5TM-C2Hn and Cl4TM-C2Hn (TM = Cr, Mo, W)Group-13 Diyl Complexes (CO)4Fe-ER ( E = B -Tl;R = Ph, Cp)Ferrocene Fe(n5-Cp)2 and Bis(benzene)chromium Cr(n6-Bz)2Cluster, Complex, or Electron-Sharing Compound? Chemical Bonding in Mo(Eh)12 and Pd(EH)8 (E = Zn, Cd, Hg)Metal-Metal Multiple BondingSummary CHEMICAL BONDING IN OPEN-SHELL TRANSITION-METAL COMPLEXESIntroductionTheoretical FoundationsQualitative InterpretationSpin Density Distributions -A Case StudySummary MODELING METAL-METAL MULTIPLE BONDS WITH MULTIREFERENCE QUANTUM CHEMICAL METHODSIntroductionMultireferance Methods and Effective Bond OrdersThe Multiple Bond in Re2Cl8 2-Homonuclear Diatomic Molecules: Cr2, Mo2, and W2Cr2, Mo2, and W2 Containing ComplexesFe2 ComplexesConcluding Remarks THE QUANTUM CHEMISTRY OF TRANSITION METAL SURFACE BONDING AND REACTIVITYIntroductionThe Elementary Quantum-Chemical Model of the Surface Chemical BondQuantum Chemistry of the Surface Chemical BondMetal Particle Composition and Size DependenceLateral Interactions;ReconstructionAdsorbate Bond Activation and FormationTransition State Analysis: A Summary CHEMICAL BONDING OF LANTHANIDES AND ACTINIDESIntroductionTechnical IssuesThe Energy Decomposition Approach to the Bonding in f Block Compoundsf Block Applications of the Electron Localization FunctionDoes Covalency Increase or Decrease across the Actinide Series?Multi-configurational Descriptions of Bonding in f Element ComplexesConcluding Remarks DIRECT ESTIMATE OF CONJUGATION, HYPERCONJUGATION, AND AROMATICITY WITH THE ENERGY DECOMPOSITION ANALYSIS METHODIntroductionThe EDA MethodConjugationHyperconjugationAromaticityConcluding Remarks MAGNETIC PROPERTIES OF AROMATIC COMPOUNDS AND AROMATIC TRANSITION STATESIntroductionA Short Historical Review of AromaticityMagnetic Properties of MoleculesExamplesConcluding Remarks CHEMICAL BONDING IN INORGANIC AROMATIC COMPOUNDSIntroductionHow to Recognize Aromaticity and Antiaromaticity?"Conventional" Aromatic/Antiaromatic Inorganic Molecules"Unconventional" Aromatic/Antiaromatic Inorganic MoleculesSummary and Perspectives CHEMICAL BONDING IN SOLIDSIntroductionElectronic Structure of Solids: Basic NotionsBonding in Solids: Some Illustrative CasesConcluding Remarks DISPERSION INTERACTION AND CHEMICAL BONDINGIntroductionA Short Survey of the Theory of the London Dispersion EnergyTheoretical Methods to Compute the Dispersion EnergySelected ExamplesConclusionComputational Details HYDROGEN BONDINGIntroductionFundamental Properties of Hydrogen BondsHydrogen Bonds with Varying StrengthsHydrogen Bonds in Biological MoleculesTheoretical Description of Hydrogen BondingSummary DIRECTIONAL ELECTROSTATIC BONDINGIntroductionAnisotropic Molecular Electrostatic Potential Distribution Around AtomsElectrostatic Anisotropy, Donor-Acceptor Interactions and PolarizationPurely Electrostatic ModelsDifference-Density TechniquesDirectional Noncovalent InteractionsConclusions Index