Electron Density and Chemical Bonding I: Experimental Charge Density Studies PDF
Preview Electron Density and Chemical Bonding I: Experimental Charge Density Studies
146 Structure and Bonding Series Editor: D. M. P. Mingos Editorial Board: F. A. Armstrong P. Day X. Duan L. H. Gade l l l K. R. Poeppelmeier G. Parkin · J.-P. Sauvage l l M. Takano Forfurthervolumes: http://www.springer.com/series/430 Structure and Bonding SeriesEditor:D.M.P.Mingos RecentlyPublishedandForthcomingVolumes ElectronDensityandChemicalBondingI Metal-MetalBonding VolumeEditor:DietmarStalke VolumeEditor:GerardParkin Vol.146,2012 Vol.136,2010 Structure-PropertyRelationshipsin FunctionalPhthalocyanineMolecular Non-LinearOpticalCrystalsII Materials VolumeEditors:Xin-TaoWu,LingChen VolumeEditor:JianzhuangJiang Vol.145,2012 Vol.135,2010 Structure-PropertyRelationshipsin DataMininginCrystallography Non-LinearOpticalCrystalsI VolumeEditors:Hofmann,D.W.M., VolumeEditors:Xin-TaoWu,LingChen Kuleshova,L.N. Vol.144,2012 Vol.134,2010 MolecularElectronicStructuresof ControlledAssemblyandModification TransitionMetalComplexesII ofInorganicSystems VolumeEditors:D.M.P.Mingos,PeterDay, VolumeEditor:Wu,X.-T. JensPederDahl Vol.133,2009 Vol.143,2012 MolecularNetworks MolecularElectronicStructuresof VolumeEditor:Hosseini,M.W. TransitionMetalComplexesI Vol.132,2009 VolumeEditors:D.M.P.Mingos,PeterDay, MolecularThermodynamics JensPederDahl ofComplexSystems Vol.142,2012 VolumeEditors:Lu,X.,Hu,Y. Vol.131,2009 FuelCellsandHydrogenStorage VolumeEditors:AndrewBocarsly, ContemporaryMetalBoronChemistryI D.M.P.Mingos VolumeEditors:Marder,T.B.,Lin,Z. Vol.141,2011 Vol.130,2008 ZintlIons RecognitionofAnions PrinciplesandRecentDevelopments VolumeEditor:Vilar,R. VolumeEditor:ThomasF.Fa¨ssler Vol.129,2008 Vol.140,2011 LiquidCrystallineFunctionalAssemblies ZintlPhases andTheirSupramolecularStructures PrinciplesandRecentDevelopments VolumeEditor:Kato,T. VolumeEditor:ThomasF.Fa¨ssler Vol.128,2008 Vol.139,2011 OrganometallicandCoordination Inorganic3DStructures ChemistryoftheActinides VolumeEditor:AngelVegas VolumeEditor:Albrecht-Schmitt,T.E. Vol.138,2011 Vol.127,2008 MolecularCatalysisofRare-EarthElements VolumeEditor:PeterW.Roesky Vol.137,2010 Electron Density and Chemical Bonding I Experimental Charge Density Studies Volume Editor: Dietmar Stalke With contributions by L.J. Farrugia U. Flierler C. Hauf V. Herz B.B. Iversen l l l l l D. Leusser P. Macchi A. Østergaard Madsen l l l J. Overgaard W. Scherer D. Stalke l l Editor DietmarStalke Universita¨tGo¨ttingen Institutfu¨rAnorganischeChemie Tammannstraße4 Go¨ttingen Germany ISSN0081-5993 ISSN1616-8550(electronic) ISBN978-3-642-30801-7 ISBN978-3-642-30802-4(eBook) DOI10.1007/978-3-642-30802-4 SpringerHeidelbergNewYorkDordrechtLondon LibraryofCongressControlNumber:2012939135 #Springer-VerlagBerlinHeidelberg2012 Thisworkissubjecttocopyright.AllrightsarereservedbythePublisher,whetherthewholeorpartofthe materialisconcerned,specificallythe rights oftranslation,reprinting, reuse ofillustrations,recitation, broadcasting,reproductiononmicrofilmsorinanyotherphysicalway,andtransmissionorinformation storageandretrieval,electronicadaptation,computersoftware,orbysimilarordissimilarmethodology nowknownorhereafterdeveloped.Exemptedfromthislegalreservationarebriefexcerptsinconnection withreviewsorscholarlyanalysisormaterialsuppliedspecificallyforthepurposeofbeingenteredand executed on a computer system, for exclusive use by the purchaser of the work. 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Printedonacid-freepaper SpringerispartofSpringerScience+BusinessMedia(www.springer.com) Series Editor Prof.D.MichaelP.Mingos InorganicChemistryLaboratory OxfordUniversity SouthParksRoad OxfordOX13QR,UK [email protected] Volume Editor DietmarStalke Universita¨tGo¨ttingen Institutfu¨rAnorganischeChemie Tammannstraße4 Go¨ttingen Germany Editorial Board Prof.FraserAndrewArmstrong Prof.XueDuan DepartmentofChemistry Director OxfordUniversity StateKeyLaboratory OxfordOX13QR ofChemicalResourceEngineering UK BeijingUniversityofChemicalTechnology 15BeiSanHuanDongLu Prof.PeterDay Beijing100029,P.R.China [email protected] DirectorandFullerianProfessor ofChemistry Prof.LutzH.Gade TheRoyalInstitutionofGreatBritain 21AlbermarleStreet Anorganisch-ChemischesInstitut LondonW1X4BS,UK Universita¨tHeidelberg [email protected] ImNeuenheimerFeld270 69120Heidelberg,Germany [email protected] vi EditorialBoard Prof.Dr.KennethR.Poeppelmeier Prof.Jean-PierreSauvage DepartmentofChemistry Faculte´ deChimie NorthwesternUniversity LaboratoiresdeChimie 2145SheridanRoad Organo-Mine´rale Evanston,IL60208-3133 Universite´LouisPasteur USA 4,rueBlaisePascal [email protected] 67070StrasbourgCedex,France [email protected] Prof.GerardParkin DepartmentofChemistry(Box3115) Prof.MikioTakano ColumbiaUniversity InstituteforIntegratedCell-Material 3000Broadway Sciences(iCeMS) NewYork,NewYork10027,USA KyotoUniversity [email protected] YoshidaUshinomiya-cho Sakyo-ku Kyoto606-8501 Japan Structure and Bonding Also Available Electronically Structure and Bonding is included in Springer’s eBook package Chemistry and MaterialsScience. If alibrarydoes notoptfor the whole package the bookseries may be bought on a subscription basis. Also, all back volumes are available electronically. For all customers who have a standing order to the print version of Structure and Bonding,weoffertheelectronicversionviaSpringerLinkfreeofcharge. Ifyoudonothaveaccess,youcanstillviewthetableofcontentsofeachvolume andtheabstractofeacharticlebygoingtotheSpringerLinkhomepage,clickingon “ChemistryandMaterialsScience,”underSubjectCollection,then“BookSeries,” underContentTypeandfinallybyselectingStructureandBonding. Youwillfindinformationaboutthe – EditorialBoard – AimsandScope – InstructionsforAuthors – SampleContribution atspringer.comusingthesearchfunctionbytypinginStructureandBonding. ColorfiguresarepublishedinfullcolorintheelectronicversiononSpringerLink. Aims and Scope The series Structure and Bonding publishes critical reviews on topics of research concerned with chemical structure and bonding. The scope of the series spans the entirePeriodicTableandaddressesstructureandbondingissuesassociatedwithall of the elements. It also focuses attention on new and developing areas of modern structural and theoretical chemistry such as nanostructures, molecular electronics, designed molecular solids, surfaces, metal clusters and supramolecular structures. Physicalandspectroscopictechniquesusedtodetermine,examineandmodelstruc- tures fall within the purview of Structure and Bonding to the extent that the focus viii StructureandBondingAlsoAvailableElectronically isonthescientificresultsobtainedandnotonspecialistinformationconcerningthe techniques themselves. Issues associated with the development of bonding models and generalizations that illuminate the reactivity pathways and rates of chemical processesarealsorelevant. Theindividualvolumesintheseriesarethematic.Thegoalofeachvolumeistogive thereader,whetheratauniversityorinindustry,acomprehensiveoverviewofanarea where new insights are emerging that are ofinterest toa larger scientific audience. Thus each review within the volume criticallysurveysone aspect ofthattopic and placesitwithinthecontextofthevolumeasawhole.Themostsignificantdevelop- mentsofthelast5to10yearsshouldbepresentedusingselectedexamplestoillustrate the principles discussed. A description of the physical basis of the experimental techniquesthathavebeenusedtoprovidetheprimarydatamayalsobeappropriate, ifithasnotbeencoveredindetailelsewhere.Thecoverageneednotbeexhaustivein data, but should rather be conceptual, concentrating on the new principles being developed that will allow the reader, who is not a specialistinthe areacovered,to understandthedatapresented.Discussionofpossiblefutureresearchdirectionsinthe areaiswelcomed. Reviewarticlesfortheindividualvolumesareinvitedbythevolumeeditors. In references Structure and Bonding is abbreviated Struct Bond and is cited as a journal. ImpactFactorin2010:4.659;Section“Chemistry,Inorganic&Nuclear”: Rank4of43;Section“Chemistry,Physical”:Rank25of127 Preface EversinceWilhelmConradRo¨ntgendiscoveredX-raysinWu¨rzburgandvonLaue, Ewald, Friedrich, Knipping, and Bragg developed analytical methods to interpret X-ray diffraction patterns a hundred years ago in Go¨ttingen, experimental single crystal structure analysis from diffraction data has become the most powerful analyticaltoolusedtoelucidateunequivocallythe threedimensional structuresof solidmatter.SincethattimethetechniquehascontributedtomanyNobelprizesin chemistry,physicsandlifesciences.Fromaknowledgeoftheconnectivitiesatthe atomic level and the arrangement in the solid phase many properties, both at the molecular and macroscopic scale, can be deduced. Currently X-ray sources in research laboratories and large facilities are getting more and more powerful, detectors more and more sensitive and crystallographic programs more and more sophisticated, so that the method continues to flourish and has been successfully appliedtoproblemsofincreasingcomplexity.However,themostbasicconcept,the chemicalbond,isstillvigorouslydiscussedandattimesdebatedsinceitsessential features were introduced by Lewis and put on a quantum mechanical basis by Pauling andMulliken. Stillthere isroomforinterpretation, because single crystal structural analyses based on the independent atom model only provides the posi- tions of the centroids of the atoms and the distances between the atoms. In the electron density maps there are no lines or dashes defining or even indicating the chemical bond and the nature of the bonding remains a matter of interpretation based on a bonding model. Hence the anecdote that a bond is where the chemist draws the line remains valid toa certain extent. Most of our understanding of the chemicalbondisstilldeducedfromthedistancesandangles,whicharedetermined as a result of the crystallographic analysis, and represents a conclusion from a logicalcausalchain.Forexample,chemicalintuitionsuggeststhatashortbondisa strongbondandpossiblyithasmultiplebondcharactermakingitdifficulttocleave, but nevertheless remaining reactive towards polar reagents. Hence we employ knowledge compiled from databases and statements of masterminds to indirectly deduce the nature of the bond. However, increasingly it has been recognised that thereareexceptionstothesesimplegeneralisations,e.g.increasing‘evidence’that shortbondsarenotnecessarilystrongormultiplebondsandmultiplebondsmayat ix x Preface times be longer than single bonds. Furthermore, there may be features of bonds whichwecannotexplainusingcurrentconcepts. This explains the increasing interest in looking at the bond directly and not by means of deductions and statistics. The Hansen and Coppens partitioning of the electron density in the aspherical atom model paved the way to describe the interference of X-rays with electrons from high resolution diffraction data more adequately. This density may then be analysed by Bader’s Quantum Theory of Atoms in Molecules, directly providing more resilient and physically meaningful descriptionsofchemicalbondingthaninferencesfrombonddistancesandangles. ThefollowingcollectionofarticlesinVolumes146and147oftheStructureand Bonding Series provides astate-of-the-art overview ofthecapacityofthemethod writtenbyleadersinthefield,whichwehopewillmotivatemorescientiststotake advantageofthegeneralapproach. Go¨ttingen DietmarStalke April2012
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