Quantum Chemistry: The Challenge of Transition Metals and Coordination Chemistry NATO ASI Series AdvancedScienceInstitutesSeries AseriespresentingtheresultsofactivitiessponsoredbytheNATOScienceCommittee, whichaimsatthedisseminationofadvancedscientificandtechnologicalknowledge, withaviewtostrengtheninglinksbetweenscientificcommunities. Theseriesispublishedbyaninternationalboardofpublishersinconjunctionwiththe NATOScientificAffairsDivision A LifeSciences PlenumPublishingCorporation B Physics LondonandNewYork C Mathematical D.ReidelPublishingCompany andPhysicalSciences Dordrecht,Boston,LancasterandTokyo D BehaviouralandSocialSciences MartinusNijhoffPublishers E Engineeringand TheHague,BostonandLancaster MaterialsSciences F ComputerandSystemsSciences Springer-Verlag G EcologicalSciences Berlin,Heidelberg,NewYorkandTokyo SeriesC:MathematicalandPhysicalSciencesVol.176 Quantum Chemistry: The Challenge of Transition Metals and Coordination Chemistry editedby A. Veillard CentreNationaldelaRechercheScientifique.Strasbourg,France D. Reidel Publishing Company Dordrecht/ Boston / Lancaster/ Tokyo PublishedincooperationwithNATOScientificAffairsDivision ProceedingsoftheNATOAdvancedResearchWorkshopandthe 40thInternationalMeetingoftheSocietedeChimiePhysique: TheChallengeofTransitionMetalsandCoordinationChemistry Strasbourg,France September16-20,1985 LibraryofCongressCataloginginPublication Data NATO Advanced Research Workshop on Quantum Chemistry, the Challenge ofTransition MetalsandCoordinationChemistry(1985:Strasbourg,France) Quantumchemistry. (NATOASI series. SeriesC, Mathematicaland physicalsciences; vol. 176)Published in cooperationwithNATOScientificAffairsDivision. "ProceedingsoftheNATOAdvanced Research Workshop(40thInternationalMeetingof theSocietedechimiephysique)onQuantumChemistry,theChallengeofTransitionMetalsand CoordinationChemistry),Strasbourg,France,September16-20,1985"- T.p.verso. Includesindex. 1. Quantum chemistry-Congresses. 2. Transition metal compounds-Congresses. 3. Coordinationcompounds-Congresses. I. Veillard, A., 1934- . II. NorthAtlantic TreatyOrganization.ScientificAffairsDivision. III. Societedechimiephysique.International Meeting(40th:1985: Strasbourg, France) IV. Title. V. Series:NATOASIseries.SeriesC, Mathematicalandphysicalsciences;vol.176. QD462.A1N16 1985 541.2'8 86-3881 ISBN-13: 978-90-277-2237-9 e-ISBN-13: 978-94-009-4656-9 DOI: 10.1007/978-94-009-4656-9 PublishedbyD.ReidelPublishingCompany P.O.Box17,3300AA Dordrecht,Holland SoldanddistributedintheU.S.A.andCanada byKluwerAcademicPublishers, 190OldDerbyStreet,Hingham,MA02043,U.SA Inallothercountries,soldanddistributed byKluwerAcademicPublishersGroup, PO.Box322,3300AH Dordrecht,Holland D.ReidelPublishingCompanyisamemberoftheKluwerAcademicPublishersGroup AllRightsReserved ©1986byD.ReidelPublishingCompany,Dordrecht,Holland. Reprintoftheoriginaledition 1986 Nopartofthematerialprotectedbythiscopyrightnoticemaybereproducedorutilized inanyformorbyanymeans,electronicormechanical,includingphotocopying,recording orbyanyinformationstorageandretrievalsystem,withoutwrittenpermissionfromthe copyrightowner. CONTENTS Preface ix ACCURATE STUDIES ON THE STRUCTURE AND REACTIVITY OF TRANSITION METAL COMPLEXES AND CLUSTERS 1 M. Blomberg, U. Brandemark, I. Panas, P. Siegbahn and U. Wahlgren THE IMPORTANCE OF ATOMIC AND MOLECULAR CORRELATION ON THE BONDING IN TRANSITION METAL COMPOUNDS 15 C. W. Bauschlicher, S.P. Walch and S.R. Langhoff THE ELECTRONIC STRUCTURE OF TRANSITION METAL ATOMS AND DIATOMS THROUGH PSEUDOPOTENTIAL APPROACHES 37 M. Pelissier, J.P. Daudey, J.P. Malrieu and G.H. Jeung SPECTROSCOPIC CHARACTERIZATION OF BONDING IN DIATOMICS AND SMALL TRANSITION METAL AGGREGATES 53 M. Tranquil1e LOW-LYING ELECTRONIC STATES OF ScH, TiH AND VH ACCORDING TO MRD-CI CALCULATIONS 67 P.J. Bruna and J. Anglada ENERGY-ADJUSTED PSEUDOPOTENTIALS FOR TRANSITION-METAL ELEMENTS 79 U. Wedig, M. Dolg, H. Stoll and H. Preuss SPECTROSCOPIC STUDIES OF COPPER COMPLEXES 91 J.C. Barthelat, M. Hliwa, G. Nicolas, M. Pelissier and F. Spiegelmann SCANDIUM ATOM INTERACTING WITH DIATOMIC GROUPS 101 G.H. Jeung THE NATURE OF THE BONDING IN THE TRANSITION METAL 119 TRIMERS S.P. Walch and C.W Bauschlicher ELECTRONIC STRUCTURE AND REACTIONS OF TRANSITION METAL COMPLEXES USING EFFECTIVE CORE POTENTIALS 135 P.J. Hay and C.M. Rohlfing vi CONTENTS CORRELATION EFFECTS IN THE GROUND AND IONIZED STATES OF TRANSITION METAL COMPLEXES 143 I.H. Hillier ANALYSIS OF a-BONDING, TI-(BACK) BONDING AND THE SYNERGIC EFFECT IN Cr(CO)6' COMPARISON OF HARTREE-FOCK AND Xa RESULTS FOR METAL-CO BONDING 159 E.J. Baerends and A. Rozendaal APPLICATIONS OF THE LCGTO-Xa METHOD TO TRANSITION METAL CARBONYLS 179 N. Rosch, H. Jorg and B.I. Dunlap QUANTITATIVE RESULTS AND QUALITATIVE ANALYSIS BY THE HARTREE-FOCK-SLATER TRANSITION STATE METHOD 189 T. Ziegler, V. Tschinke and L. Versluis Xa ELECTRONIC STRUCTURE OF TRANSITION METAL HALIDES CALCULATION OF LIGAND-FIELD MULTIPLET STATES 199 A. Goursot and C. Daul COMPLEMENTARY SPHERICAL ELECTRON DENSITY MODEL FOR COORDINATION AND ORGANOMETALLIC COMPOUNDS 209 D.M.P. Mingos THEORETICAL ANALYSIS OF BONDING PROPERTIES IN TRANSITION METAL COMPLEXES. LIGAND SUBSTITUTION EFFECTS 225 L.G. Vanquickenborne, I. Hyla-Kryspin and M. Hendrickx TOPOLOGY OF POTENTIAL ENERGY SURFACES : THE COMPLEMENTARITY OF MO AND VB APPROACHES 235 A. Sevin APPLIED MO THEORY ORGANOMETALLIC STRUCTURE AND REACTIVITY PROBLEMS 253 P. Hofmann CO ACTIVATION AND REACTIVITY IN ORGANOMETALLIC CHEMISTRY : THEORETICAL STUDIES 277 A. Dedieu and S. Nakamura STRUCTURAL DISTORTIONS AND ACTIVATION OF A C-H BOND IN dO ELECTRON DEFICIENT ALKYL TRANSITION METAL COMPLEXES 301 A. Demolliens, Y. Jean and O. Eisenstein STEREOCHEMISTRY AND METAL-LIGAND INTERACTION OF GROUP VIII LOW-VALENT TRANSITION METAL COMPLEXES. AN AB INITIO MO AND ENERGY DECOMPOSITION ANALYSIS STUDY 319 S. Sakaki CONTENTS vii STABILIZATION OF PHOSPHINIDENE AND PHOSPHIRENE BY COMPLEXATION ON PHOSPHORUS. THEORETICAL AND PHOTO ELECTRON STUDIES 333 G. Pfister-Guillouzo and D. Gonbeau MOLECULAR ORBITAL CALCULATIONS ON METALLOCENES WITH UNUSUAL GEOMETRIES 341 T.A. Albright, J.P. Lopez and J. Silvestre TRANSITION STATE FOR CARBONYL AND OLEFIN INSERTION REACTIONS 351 N. Koga and K. Morokuma THEORETICAL ASPECTS OF THE PHOTOCHEMISTRY OF ORGANO METALLICS 363 C. Daniel and A. Veillard ELECTRONIC STRUCTURE OF METALLOPORPHYRINS AB INITIO CI CALCULATIONS 377 M.-M. Rohmer MULTIPLE METAL-METAL AND METAL-CARBON BONDS 391 M.B. Hall DESIGN OF FERROMAGNETICALLY COUPLED POLYMETALLIC SYSTEMS TOWARD THE MOLECULAR FERROMAGNETS 403 O. Kahn A SPECTROSCOPIC AND MAGNETIC INVESTIGATION OF MX 4 4 CLUSTERS : LOCALIZED OR ITINERANT ELECTRONS? 413 C.E. Davies, J.C. Green and G.H. Stringer MOVING FROM DISCRETE MOLECULES TO EXTENDED STRUCTURES A CHEMICAL AND THEORETICAL APPROACH TO THE SOLID STATE 425 R. Hoffmann and C. Zheng CLUSTER-SURFACE ANALOGY : NEW DEVELOPMENTS 445 E. Shustorovich CLUSTER MODEL CALCULATIONS OF THE INTERACTION OF HAND CO WITH SMALL Pd CLUSTERS 465 G. Pacchioni and J. Koutecky THEORETICAL STUDY ON THE CATALYTIC ACTIVITIES OF PALLADIUM FOR THE HYDROGENATION REACTION OF ACETYLENE 477 H. Nakatsuji and M. Hada THEORETICAL STUDY OF THE SUCCESSIVE HYDROGENATION OF SMALL PLATINUM CLUSTERS 489 B. Bigot and C. Minot viii CONTENTS PARTICIPANTS 501 INDEX 515 PREFACE Over the last twenty years, developments of the ab initio metho dologies and of the computing capacities have progressively turned quantum chemistry into a predictive tool for molecular systems involving only light elements. The situation appears less advanced for systems containing transition metal elements where specific difficulties arise, like those 1inked to the quasi-degeneracy of the lowest atomic states. Correlation effects, which are important only for quantitative accuracy in the treatment of molecules made of light elements, need sometimes to be considered even for a qualitative des cription of transition metals systems (like the multiple metal-metal bond). The treatment of atoms of a high atomic number has necessited the development of model potential methods. These difficulties ex acerbate for systems containing several transition atoms a correct description of the dichromium molecule Crz still represents a challenge to quantum chemists. Yet many advances have been made recently in the theoretical treatment of these systems, despite the fact that our understanding still remains disparate with a variety of models and methodologies used more or less successfully (one-electron models, explicitly correlated ab initio methods, density functional formalisms). For these reasons, a NATO Advanced Research Workshop was organized to review in detail the state-of-the-art techniques and at the same time the most common applications. These encompass many fields including the spectroscopy of diatomics and small aggregates, structure and reactivity problems in organometallic chemistry, the cluster surface analogy with its implications for heterogeneous catalysis and the description of extended structures. This conference was patronized jointly by NATO and by the Societe de Chimie Physique (40th International Meeting). The organizing committee consisted of Drs. E. Baerends, A. Dedieu, O. Eisenstein, I. Hillier, P. Hofmann, J.-P. Malrieu, C. Minot, M. Pelissier, P. Siegbahn and myself. It was financially sponsored by the NATO Scientific Affairs Division. It also benefited from the financial assistance of the Centre National de la Recherche Scientifique, the Societe Fran<;aise de Chimie, Cray Research France and the Conseil General du Bas-Rhin. We gratefully acknowledge their generous support and their interest in the meeting. A. Veillard i:I: ACCURATE STUDIES ON THE STRUCTURE AND REACTnnTY OF TRANSITION METAL COMPLEXES AND CLUSTERS M. Blomberg, U. Brandemark, 1. Panas, P. Siegbahn and U. Wahlgren Institute of Theoretical Physics University of Stockholm Vanadisvagen 9 S-11346 Stockholm Sweden ABSTRACT. Three different applications of CASSCF and CI methods on transition metal systems are described. The first application is concerned with the accuracy of calculated binding energies. For NiH+ and NiO+ comparison is made to molecular beam experiments. For NiCO+ and NjCO comparisons are made to measurements of appearence potentials in fragmentation experiments. In the second application comparisons are made to matrix isolation experiments for NiH 0, 2 CuH 0 and Ni(C H,t)n with n=l,2. The final application is 2 2 concerned with tfie modelling of chemical reactions on transition metal surfaces. A strategy for choosing a proper effective core potential for the metal atoms is outlined. Preliminary results for 02 dissociation on nickel clusters are presented. 1. INTRODUCTION The present contribution will describe the recent research on transition metal compounds, which has been performed in the quantum chemistry group in Stockholm. This work is part of the more general project with a goal to obtain a fundamental understanding of chemical reactions involving transition metals using methods including electron correlation. This general project started with a detailed study of potential curves and spectrum of NiH [1] and continued with a similar detailed study of NiH [2]. Important chemical implications were 2 found already from tlilS very simple model system. It was found that the 1> state of nickel binds quite differently to H than the triplet 2 states. The lowest singlet state has a shallow minimum with practically no barrier for formation, whereas the triplet states all have large barriers. The behaviour of the singlet state is characteristic also for what is found experimentally for H addition to nickel complexes and 2 for H dissociation on nickel surfaces. It was therefore concluded that ~e singlet state is the chemically most relevant state, and in all subsequent calculations on larger systems this is the state that has been mainly considered. It is clear that there is a similarity between the single atom results for Ni + H and for what is observed 2 A.Vei/lard(ed.), QuantumChemistry:TheChallengeofTransitionMetalsandCoordinationChemistry, 1-14. ©1986 byD.ReidelPublishingCompany.