Table Of Content

SpringerSeriesin chemical physics 83 SpringerSeriesin chemical physics SeriesEditors: A.W.Castleman,Jr. J.P.Toennies W.Zinth The purpose of this series is to provide comprehensive up-to-date monographs inbothwellestablisheddisciplinesandemergingresearchareaswithinthebroad fieldsofchemicalphysicsandphysicalchemistry.Thebooksdealwithbothfun- damentalscienceandapplications,andmayhaveeitheratheoreticaloranexperi- mentalemphasis.Theyareaimedprimarilyatresearchersandgraduatestudents inchemicalphysicsandrelatedfields. 69 SelectiveSpectroscopy 77 HeterogeneousKinetics ofSingleMolecules TheoryofZiegler-Natta-Kaminsky ByI.S.Osad’ko Polymerization 70 Chemistry ByT.Keii ofNanomolecularSystems 78 NuclearFusionResearch TowardstheRealization UnderstandingPlasma-Surface ofMolecularDevices Interactions Editors:T.Nakamura, Editors: R.E.H. Clark and D.H. T.Matsumoto,H.Tada, Reiter K.-I.Sugiura 79 UltrafastPhenomenaXIV 71 UltrafastPhenomenaXIII Editors:T.Kobayashi, Editors:D.Miller,M.M.Murnane, T.Okada,T.Kobayashi, N.R.Scherer,andA.M.Weiner K.A.Nelson,S.DeSilvestri 72 PhysicalChemistry 80 X-RayDiffraction ofPolymerRheology byMacromolecules ByJ.Furukawa ByN.KasaiandM.Kakudo 73 OrganometallicConjugation 81 Advanced Time-Correlated Single Structures,Reactions PhotonCountingTechniques andFunctionsofd–d ByW.Becker andd–πConjugatedSystems 82 TransportCoefficientsofFluids Editors:A.Nakamura,N.Ueyama, ByB.C.Eu andK.Yamaguchi 83 Quantum Dynamics of Complex 74 SurfaceandInterfaceAnalysis MolecularSystems AnElectrochmistsToolbox Editors:D.A.Micha ByR.Holze andI.Burghardt 75 BasicPrinciples 84 ProgressinUltrafast inAppliedCatalysis IntenseLaserScienceI ByM.Baerns Editors:K.Yamanouchi,S.L.Chin, 76 TheChemicalBond P.Agostini,andG.Ferrante AFundamental 85 ProgressinUltrafast Quantum-MechanicalPicture IntenseLaserScienceII ByT.Shida Editors:K.Yamanouchi,S.L.Chin, P.Agostini,andG.Ferrante D.A. Micha I. Burghardt (Eds.) Quantum Dynamics of Complex Molecular Systems With99Figures, 9 in Color and 7 Tables 123 Dr.DavidA.Micha,ProfessorofChemistryandPhysics UniversityofFlorida P.O.Box118435,2318NewPhysicsBldg.,GainesvilleFL32611-8435,USA E-Mail:[email protected]fl.edu Dr.IreneBurghardt D ép artementdeChimie,EcoleN ormaleSupérieure 24rueLhomond,F-75231Pariscedex05,France E-Mail:[email protected] SeriesEditors: ProfessorA.W.Castleman,Jr. DepartmentofChemistry,ThePennsylvaniaStateUniversity 152DaveyLaboratory,UniversityPark,PA16802,USA ProfessorJ.P.Toennies Max-Planck-InstitutfürStro¨mungsforschung,Bunsenstrasse10 37073Go¨ttingen,Germany ProfessorW.Zinth Universita¨tMu¨nchen,Institutfu¨rMedizinischeOptik O¨ttingerstr.67,80538Mu¨nchen,Germany ISSN0172-6218 ISBN-103-540-34458-6SpringerBerlinHeidelbergNewYork ISBN-13978-3-540-34458-2SpringerBerlinHeidelbergNewYork LibraryofCongressControlNumber:2006928272 This work is subject to copyright. All rights are reserved, whether the whole or part of the material is concerned,specificallytherightsoftranslation,reprinting,reuseofillustrations,recitation,broadcasting, reproductiononmicrofilmorinanyotherway,andstorageindatabanks.Duplicationofthispublicationor partsthereofispermittedonlyundertheprovisionsoftheGermanCopyrightLawofSeptember9,1965,in itscurrentversion,andpermissionforusemustalwaysbeobtainedfromSpringer.Violationsareliableto prosecutionundertheGermanCopyrightLaw. SpringerisapartofSpringerScience+BusinessMedia. springer.com ©Springer-VerlagBerlinHeidelberg2007 Theuseofgeneraldescriptivenames,registerednames,trademarks,etc.inthispublicationdoesnotimply, evenintheabsenceofaspecificstatement,thatsuchnamesareexemptfromtherelevantprotectivelawsand regulationsandthereforefreeforgeneraluse. TypesettingbytheauthorsandSPi usingaSpringerLATEXmacropackage Coverconcept:eStudioCalamarSteinen Coverproduction: WMXDesignGmbH,Heidelberg Printedonacid-freepaper SPIN:11502227 54/3100/SPi-543210 Preface Quantum phenomena are ubiquitous in complex molecular systems, and yet remain a challenge for theoretical analysis. A complex molecular system is composedofmanyatomsandmayforexampleconstituteanassemblyofmole- cules, a cluster, a polymer, a chromophore-protein complex, or an adsorbate- surface structure. The system may be isolated, or more likely in contact with some physical environment. Its properties and behavior usually depend on the way it interacts with external fields or with other molecular species, and typically involve excited atomic and electronic states, which must be described in terms of quantum mechanics. From the point of view of quantum theory, one is dealing with a system with many quantized degrees of freedom, a subject that has been formally explored for a long time. But molecular systems are special, in that they involve particles (electrons and nuclei) with very different masses leading to interactions with very different time scales. Therefore, quantum molecular dynamics can often be described in terms of potential energy surfaces within the Born–Oppenheimer approximation – even though it is the breakdown of this approximation, at avoided crossings or conical intersections, which is at the root of many reactive and photochemical processes. Further, molecular systems are subject to thermo- dynamical constraints when they interact with a medium, which in turn dy- namicallyevolvesasaresultoftheinteractionwiththemolecularsubsystem. The subsystem’s quantum dynamics is thus entangled with the nonequilib- rium evolution of the environment. Due to these many facets of dynamical behavior, the quantum dynamics of molecular systems, including statistical effects, has become one of the most challenging and active areas of molecular science. Muchcurrentactivityisdirectedatdevelopingmethodstotacklequantum dynamics in many dimensions, including quantum coherence and dissipative phenomena,oftenwiththeaimofinterpretingandpredictingexperimentalob- servations based upon detailed molecular scattering experiments or ultrafast spectroscopic techniques. Indeed, the direct, femtosecond scale, observation VI Preface of molecular phenomena (“femtochemistry”) has given a strong impetus to the theoretical and computational developments in quantum dynamics. Applications and comparisons with experiments demand theories that can be implemented numerically to calculate measurable properties. Straightforward numerical methods for solving the differential equations of quantum mechanics, based on basis set expansions or discretization of variables on a grid, are restricted to small systems and are not practical for complex molecular systems. Relevant and useful treatments include self-consistent field methods for atomic motions and their multiconfiguration extensions, path integral methods for molecular motions, semiclassical and mixed quantum–classical approaches, various trajectory based methods, and density matrix methods describing both population relaxation and decoherence. Thepresentbook grewoutof aworkshop organized in May 2005 in Paris, France,tobringtogetherworkersinthefieldofquantumdynamicsofmolecu- larsystems,todiscussapplicationsofpresenttheoriestoavarietyofphenom- ena,alongwithnewtheoreticalconceptsandmethods.Thefollowingchapters havebeencontributedbysomeoftheworkshopparticipantsandtheircollab- orators, and have been grouped in what follows into Part I, with applications to complex molecular systems, and Part II, on new theoretical and computational methods. In fact, method development and applications are closely interconnected and related work is found in both parts. Much can be done to explain phenomena in systems excited by light or throughatomicinteractions,extendingfromthemolecularscaletonanoscales andeventomacroscopicdimensions.Thefollowingchaptersshowthatpromis- ingnewmethodsarenowavailableforthosepurposes.Theydemonstratehow one can tackle the multidimensional dynamics arising from the atomic structure of a complex system, and address phenomena in condensed phases as well as phenomena at surfaces. The chapters on new methodological developments cover both phenomena in isolated systems, and phenomena that involve the statistical effects of an environment, such as fluctuations and dissipation. The methodology part explores new rigorous ways to formulate mixedquantum–classicaldynamicsinmanydimensions,alongwithnewways to solve a many-atom Schrödinger equation, or the Liouville-von Neumann equation for the density operator, using trajectories and ideas related to hydrodynamics. The workshop leading to this book was made possible by sponsors from the University of Florida in the USA and by several institutions in France. We thank in connection with the University of Florida: the Paris Research Center, the Vice President for Research, the Quantum Theory Project (an Institute for Theory and Computation in the Molecular and Materials Sci- ences), and the Chemistry and Physics Departments. On the French side, we thank the Centre National de la Recherche Scientifique (CNRS), the Min- istèredel’EducationNationale,theEcoleNormaleSupérieure,Paris,andthe EcoleDoctorale388“ChimiePhysiqueetChimieAnalytique.”Theworkshop Preface VII greatlyprofitedfromthesupportoftheDirectoroftheParisResearchCenter, Dr. Gayle Zachmann, and from the help of Rachel Gora. We appreciate their enthusiasm and hospitality. Gainesville (Florida), USA David A. Micha Paris, France Irene Burghardt July 2006 Contents Part I Complex Molecular Phenomena I.1 Condensed Matter and Surface Phenomena Photoexcitation Dynamics on the Nanoscale O.V. Prezhdo, W.R. Duncan, C.F. Craig, S.V. Kilina, and B.F. Habenicht ....................................................... 5 Ultrafast Exciton Dynamics in Molecular Systems B. Bru¨ggemann, D. Tsivlin, and V. May............................ 31 Exciton and Charge-Transfer Dynamics in Polymer Semiconductors Eric R. Bittner and John Glen S. Ramon ........................... 57 Dynamics of Resonant Electron Transfer in the Interaction Between an Atom and a Metallic Surface J.P. Gauyacq and A.G. Borisov.................................... 87 I.2 From Multidimensional Dynamics to Dissipative Phenomena Nonadiabatic Multimode Dynamics at Symmetry-Allowed Conical Intersections H. Ko¨ppel.......................................................113 Non-Markovian Dynamics at a Conical Intersection: Ultrafast Excited-State Processes in the Presence of an Environment I. Burghardt.....................................................135 Density Matrix Treatment of Electronically Excited Molecular Systems: Applications to Gaseous and Adsorbate Dynamics D.A. Micha, A. Leathers, and B. Thorndyke.........................165 X Contents Quantum Dynamics of Ultrafast Molecular Processes in a Condensed Phase Environment M. Thoss, I. Kondov, and H. Wang ................................195 Part II New Methods for Quantum Molecular Dynamics in Large Systems II.1 Semiclassical Methods Decoherence in Combined Quantum Mechanical and Classical Mechanical Methods for Dynamics as Illustrated for Non-Born–Oppenheimer Trajectories Donald G. Truhlar ...............................................227 Time-Dependent, Direct, Nonadiabatic, Molecular Reaction Dynamics Y. O¨hrn and E. Deumens.........................................245 The Semiclassical Initial Value Series Representation of the Quantum Propagator Eli Pollak.......................................................259 II.2 Mixed Quantum-Classical Statistical Mechanics Methods Quantum Statistical Dynamics with Trajectories G. Ciccotti, D.F. Coker, and Raymond Kapral.......................275 Quantum–Classical Reaction Rate Theory G. Hanna, H. Kim, and R. Kapral .................................295 Linearized Nonadiabatic Dynamics in the Adiabatic Representation D.F. Coker and S. Bonella ........................................321 II.3 Quantum Trajectory Methods Atom–Surface Diffraction: A Quantum Trajectory Description A.S. Sanz and S. Miret-Artés......................................343 Hybrid Quantum/Classical Dynamics Using Bohmian Trajectories C. Meier and J.A. Beswick........................................369 Quantum Hydrodynamics and a Moment Approach to Quantum–Classical Theory I. Burghardt, K.B. Møller, and K.H. Hughes ........................391 Index..........................................................423 List of Contributors J.A. Beswick I. Burghardt Laboratoire Collisions Agrégats Département de Chimie Réactivité, IRSAMC Ecole Normale Supérieure Université Paul Sabatier 24 rue Lhomond Toulouse, France F–75231 Paris, France [email protected] [email protected] E.R. Bittner G. Ciccotti DepartmentofChemistryandCenter for Materials Chemistry Dipartmento di Fisica University of Houston Università “La Sapienza” Houston, TX, USA Piazzale Aldo Moro 2 [email protected] 00185 Rome, Italy [email protected] S. Bonella NEST Scuola Normale Superiore D.F. Coker Piazza dei Cavalieri 7 Department of Chemistry It-56126 Pisa, Italy Boston University [email protected] 590 Commonwealth Avenue A.G. Borisov Boston, MA 02215, USA Laboratoire des Collisions [email protected] Atomiques et Moléculaires UMR CNRS-Université Paris-Sud C.F. Craig 8625 Department of Chemistry Bât. 351 Université Paris-Sud University of Washington 91405 Orsay Cedex, France Seattle, WA 98195-1700, USA B. Bru¨ggemann Chemical Physics, Lund University E. Deumens P.O. Box 124 SE–22100 University of Florida Lund Sweden Gainesville, FL 32611-8435, USA [email protected] [email protected]