Table Of ContentSpringerSeriesin
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
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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 quan-
tum 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 approx-
imation – 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 mechan-
ics, 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 meth-
ods 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 compu-
tational 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 struc-
ture of a complex system, and address phenomena in condensed phases as
well as phenomena at surfaces. The chapters on new methodological devel-
opments 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 Schr¨odinger 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-
ist`eredel’EducationNationale,theEcoleNormaleSup´erieure,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-Art´es......................................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 Agr´egats D´epartement de Chimie
R´eactivit´e, IRSAMC Ecole Normale Sup´erieure
Universit´e 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 Universit`a “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 Mol´eculaires
UMR CNRS-Universit´e Paris-Sud C.F. Craig
8625
Department of Chemistry
Bˆat. 351 Universit´e 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]
