Handbook of Relativistic Quantum Chemistry PDF
Preview Handbook of Relativistic Quantum Chemistry
Wenjian Liu Editor Handbook of Relativistic Quantum Chemistry Handbook of Relativistic Quantum Chemistry Wenjian Liu Editor Handbook of Relativistic Quantum Chemistry With150Figuresand87Tables 123 Editor WenjianLiu BeijingNationalLaboratoryforMolecularSciences InstituteofTheoreticalandComputationalChemistry StateKeyLaboratoryofRareEarthMaterialsChemistry andApplications CollegeofChemistryandMolecularEngineering,and CenterforComputationalScienceandEngineering PekingUniversity Beijing,People’sRepublicofChina ISBN:978-3-642-40765-9 ISBN:978-3-642-40766-6(eBook) ISBN:978-3-642-40767-3(printandelectronicbundle) DOI10.1007/978-3-642-40766-6 LibraryofCongressControlNumber:2016950439 ©Springer-VerlagBerlinHeidelberg2017 Thisworkissubjecttocopyright.AllrightsarereservedbythePublisher,whetherthewholeorpartof thematerialisconcerned,specificallytherightsoftranslation,reprinting,reuseofillustrations,recitation, broadcasting,reproductiononmicrofilmsorinanyotherphysicalway,andtransmissionorinformation storageandretrieval,electronicadaptation,computersoftware,orbysimilarordissimilarmethodology nowknownorhereafterdeveloped. Theuseofgeneraldescriptivenames,registerednames,trademarks,servicemarks,etc.inthispublication doesnotimply,evenintheabsenceofaspecificstatement,thatsuchnamesareexemptfromtherelevant protectivelawsandregulationsandthereforefreeforgeneraluse. Thepublisher,theauthorsandtheeditorsaresafetoassumethattheadviceandinformationinthisbook arebelievedtobetrueandaccurateatthedateofpublication.Neitherthepublishernortheauthorsor theeditorsgiveawarranty,expressorimplied,withrespecttothematerialcontainedhereinorforany errorsoromissionsthatmayhavebeenmade. Printedonacid-freepaper ThisSpringerimprintispublishedbySpringerNature TheregisteredcompanyisSpringer-VerlagGmbHGermany Theregisteredcompanyaddressis:HeidelbergerPlatz3,14197Berlin,Germany Preface Just two years after Schrödinger proposed in 1926 the (nonrelativistic) quantum mechanical wave equation of electrons, Dirac established in 1928 the relativistic counterpartbyfirstquantizingthespecialtheoryofrelativitysetupbyEinsteinin 1905. Any difference between the Dirac and Schrödinger equations of electrons was then called “relativistic effect.” However, just one year later, that is, in 1929, Dirac himself stated that “relativistic effects are of no importance in the consideration of atomic and molecular structure and ordinary chemical reactions.” The underlying assumptions were that the average speeds of valence electrons are verylowcomparedwiththatoflight,suchthatrelativisticeffectsareverysmallfor valenceelectrons,andthatrelativisticeffectsareindeedimportantforcoreelectrons but are canceled out for valence properties. Such wrong assumptions were taken naivelyforgrantedfornearlyhalfacentury,untilthemid-1970s,whenrelativistic effectswerefoundtobeindeedveryimportantforelectronicstructure,sometimes even of light atoms. Since then, relativistic quantum chemistry witnessed fast progresses, including deep understandings of not only relativistic effects but also novelapproximatetwo-component(A2C)relativistictheoriessuchassecond-order DKH (Douglass-Kroll-Hess), ZORA (zeroth-order regular approximation), and DPT(directperturbationtheory)developedbetween1985and1995.Thebeginning ofthenewmillenniumturnedouttobealsothebeginningofaneweraofrelativistic quantum chemistry, as symbolized by the exact two-component (X2C) relativistic theoryintroducedandmadematurebetween2005and2010.Undoubtedly,X2Cis goingtobethenewworkhorseofrelativisticquantumchemistry.Notwithstanding thisachievement,theno-pairapproximationunderlyingbothA2CandX2Ctheories has some fundamental defects. How to go beyond this approximation yet without diving into full quantum electrodynamics (QED) is then the final high point of relativistic quantum chemistry. After several unsuccessful tries, a proper effective QED (eQED) approach was finally obtained in a bottom-up fashion, i.e., without recoursetoQEDitselfatall.ThiseQEDpavesaseamlessbridgebetweenrelativistic quantumchemistryandfullQED,whichusedtobetwomutuallyexclusivesubfields of relativistic molecular quantum mechanics. In the subfield of QED, both new formulations and applications have been achieved in the last decade. Especially, effective means to combine QED with many-body theory have been designed to achieveunprecedentedhighaccuracyinspectroscopiccalculations. v vi Preface All the aforementioned fundamental developments in relativistic molecular quantum mechanics, the union of relativistic quantum chemistry and QED, are fully covered by this book but otherwise not covered by any other books. To facilitate understandings of such methodological developments, sufficient peda- gogic introductions are also provided. Therefore, the book should be useful for both users and developers of relativistic quantum mechanical methods and tools. It is somewhat unfortunate that a collection of representative applications of such methods,althoughplanned,wasnotyetaccomplishedbutwhichwillbeincludedin aneweditionofthebook. The editor is very grateful to the section editors for their efforts in identifying excellent chapter writers. The editorial team wants to acknowledge the chapter writers for their great contributions and also the staff of Springer, including June, Neha,andStephen,whosepatienceandprofessionalcopyeditwereofgreathelpto materializethebook. Beijing WenjianLiu September2016 Contents PartI IntroductiontoRelativisticQuantumChemistry .............. 1 Christoph van Wüllen 1 DiracOperatorandItsProperties ............................... 3 JacekKarwowski 2 NuclearChargeDensityandMagnetizationDistributions ........... 51 DirkAndrae 3 One-ParticleBasisSetsforRelativisticCalculations ................ 83 KennethG.Dyall 4 RelativisticSelf-ConsistentFields................................107 ChristophvanWüllen PartII IntroductiontoQuantumElectrodynamics .................. 129 Paul Indelicato 5 IntroductiontoBound-StateQuantumElectrodynamics ............131 PaulIndelicatoandPeterJ.Mohr 6 QEDEffectsandChallenges ....................................243 AntonN.Artemyev 7 EffectiveQEDHamiltonians ....................................267 AntonN.Artemyev 8 Two-TimeGreensFunctionMethod..............................287 AntonN.Artemyev 9 Unifying Many-Body Perturbation Theory withQuantumElectrodynamics .................................313 IngvarLindgrenandPaulIndelicato PartIII RelativisticHamiltonians ................................. 343 Wenjian Liu 10 With-PairRelativisticHamiltonians..............................345 WenjianLiu vii viii Contents 11 No-PairRelativisticHamiltonians:Q4CandX2C..................375 WenjianLiu 12 Sequential Decoupling of Negative-Energy States in Douglas–Kroll–HessTheory ....................................395 MarkusReiher 13 SpinSeparationofRelativisticHamiltonians ......................411 ZhendongLiandWenjianLiu 14 RelativisticEffectiveCorePotentials .............................449 MichaelDolg PartIV RelativisticWaveFunctionsandDensityFunctionals ......... 479 Wenjian Liu 15 BasicStructuresofRelativisticWaveFunctions....................481 SihongShao,ZhendongLi,andWenjianLiu 16 CoalescenceConditionsofRelativisticWaveFunctions .............497 SihongShao,ZhendongLi,andWenjianLiu 17 RelativisticExplicitCorrelation:ProblemsandSolutions ...........531 WenjianLiu,SihongShao,andZhendongLi 18 RelativisticDensityFunctionalTheory ...........................547 EberhardEngel PartV RelativisticQuantumChemicalMethodsandApplications .... 579 Jochen Autschbach and Jun Li 19 RelativisticMany-BodyAspectsofthe ElectronElectricDipoleMomentSearchesUsingMolecules .........581 Bhanu P. Das, Malaya Kumar Nayak, Minori Abe, and V.S.Prasannaa 20 RelativisticCalculationsofAtomicClock .........................611 BijayaKumarSahoo 21 RelativisticTheoriesofNMRShielding...........................657 YunlongXiao,WenjianLiu,andJochenAutschbach 22 RelativisticTheoryofNuclearSpin-RotationTensor ...............693 YunlongXiao,WenjianLiu,andKennethRuud 23 RelativisticMethodsforCalculating ElectronParamagneticResonance(EPR)Parameters ..............725 HélèneBolvinandJochenAutschbach Contents ix 24 Zero-Field Splitting in Transition Metal Complexes: AbInitioCalculations,EffectiveHamiltonians,Model Hamiltonians,andCrystal-FieldModels..........................765 Rémi Maurice, Ria Broer, Nathalie Guihéry, and CoendeGraaf 25 RelativisticEquation-of-MotionCoupled-Cluster Theory(EOM-CC) ............................................797 FanWang 26 High-AccuracyRelativisticCoupled-ClusterCalculations fortheHeaviestElements.......................................825 EphraimEliav,AnastasiaBorschevsky,andUziKaldor 27 RelativisticQuantumChemistryforChemical IdentificationoftheSuperheavyElements ........................857 ValeriaPershina Index ............................................................901
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