Advances in the Theory of Atomic and Molecular Systems: Dynamics, Spectroscopy, Clusters, and Nanostructures

288 Pages·2009·12.63 MB·english

by  Yasuteru Shigeta

ADVANCESINTHETHEORYOFATOMIC
ANDMOLECULARSYSTEMS
Progress in Theoretical Chemistry and Physics
VOL UME 20
Honorary Editors:
W.N. Lipscomb (Harvard University, Cambridge, MA, U.S.A.)
Yves Chauvin (Institut Français du Pétrole, Tours, France )
Editors-in-Chief:
J. Maruani (formerly Laboratoire de Chimie Physique, Paris, France)
S. Wilson (formerly Rutherford Appleton Laboratory, Oxfordshire, U.K.)
Editorial Board:
V. Aquilanti (Università di Perugia, Italy)
E. Brändas (University of Uppsala, Sweden)
L. Cederbaum (Physikalisch-Chemisches Institut, Heidelberg, Germany)
G. Delgado-Barrio (Instituto de Matemáticas y Física Fundamental, Madrid, Spain)
E.K.U. Gross (Freie Universität, Berlin, Germany)
K. Hirao (University of Tokyo, Japan)
R. Lefebvre (Université Pierre-et-Marie-Curie, Paris, France)
R. Levine (Hebrew University of Jerusalem, Israel)
K. Lindenberg (University of California at San Diego, CA, U.S.A.)
M. Mateev (Bulgarian Academy of Sciences and University of Sofia, Bulgaria)
R. McWeeny (Università di Pisa, Italy)
M.A.C. Nascimento (Instituto de Química, Rio de Janeiro, Brazil)
P. Piecuch (Michigan State University, East Lansing, MI, U.S.A.)
S.D. Schwartz (Yeshiva University, Bronx, NY, U.S.A.)
A. Wang (University of British Columbia, Vancouver, BC, Canada)
R.G. Woolley (Nottingham Trent University, U.K.)
Former Editors and Editorial Board Members:
ˆ
I. Prigogine (†) I. Hubac(*)
J. Rychlewski (†) M.P. Levy (*)
Y.G. Smeyers (†) G.L. Malli(*)
R. Daudel (†) P.G. Mezey (*)
H. Ågren (*) N. Rahman (*)
D. Avnir (*) S. Suhai(*)
J. Cioslowski (*) O. Tapia(*)
W.F. van Gunsteren (*) P.R. Taylor (*)
†: deceased; * : end of term
For other titles published in this series, go to
www.springer.com/series/6464
Advances in the Theory of Atomic
and Molecular Systems
Dynamics, Spectroscopy, Clusters,
and Nanostructures
Editedby
PIOTRPIECUCH
MichiganStateUniversity,EastLansing,MI,USA
JEANMARUANI
CNRS,Paris,France
GERARDODELGADO-BARRIO
CSIC,Madrid,Spain
and
STEPHENWILSON
UniversityofOxford,UK
Editors
PiotrPiecuch JeanMaruani
DepartmentofChemistry LaboratoiredeChimiePhysique
MichiganStateUniversity CNRSandUPMC
EastLansing,MI48824 11RuePierreetMarieCurie
USA F-75005Paris
[email protected] France
[email protected]
[email protected]
GerardoDelgado-Barrio StephenWilson
InstitutodeF´ısicaFundamental Physical&TheoreticalChemistryLaboratory
CSIC UniversityofOxford
Serrano123 SouthParksRoad
E-28006Madrid OxfordOX13QZ
Spain UnitedKingdom
[email protected] [email protected]
ISSN1567-7354
ISBN978-90-481-2984-3 e-ISBN978-90-481-2985-0
DOI10.1007/978-90-481-2985-0
SpringerDordrechtHeidelbergLondonNewYork
LibraryofCongressControlNumber:2009929297
(cid:2)c SpringerScience+BusinessMediaB.V.2009
Nopartofthisworkmaybereproduced,storedinaretrievalsystem,ortransmittedinanyformorby
anymeans,electronic,mechanical,photocopying,microfilming,recordingorotherwise,withoutwritten
permissionfromthePublisher,withtheexceptionofanymaterialsuppliedspecificallyforthepurpose
ofbeingenteredandexecutedonacomputersystem,forexclusiveusebythepurchaserofthework.
Printedonacid-freepaper
SpringerispartofSpringerScience+BusinessMedia(www.springer.com)
Progress in Theoretical Chemistry and Physics
Aseriesreportingadvancesintheoreticalmolecularandmaterialssciences,includ-
ingtheoretical,mathematicalandcomputationalchemistry,physicalchemistry,and
chemicalphysics
AimandScope
Scienceprogressesbyasymbioticinteractionbetweentheoryandexperiment:the-
ory is used to interpret experimental results and may suggest new experiments;
experimenthelpstotesttheoreticalpredictionsandmayleadtoimprovedtheories.
Theoretical Chemistry (including Physical Chemistry and Chemical Physics) pro-
videstheconceptualandtechnicalbackgroundandapparatusfortherationalization
of phenomena in the chemical sciences. It is, therefore, a wide ranging subject,
reflecting the diversity of molecular and related species and processes arising in
chemicalsystems.ThebookseriesProgressinTheoreticalChemistryandPhysics
aimstoreportadvancesinmethodsandapplicationsinthisextendeddomain.Itwill
comprisemonographsaswellascollectionsofpapersonparticularthemes,which
mayarisefromproceedingsofsymposiaorinvitedpapersonspecifictopicsaswell
asinitiativesfromauthorsortranslations.
Thebasictheoriesofphysics–classicalmechanicsandelectromagnetism,rela-
tivitytheory,quantummechanics,statisticalmechanics,quantumelectrodynamics–
support the theoretical apparatus which is used in molecular sciences. Quantum
mechanics plays a particular role in theoretical chemistry, providing the basis for
the valence theories which allow to interpret the structure of molecules and for
the spectroscopic models employed in the determination of structural information
fromspectralpatterns.Indeed,QuantumChemistryoftenappearssynonymouswith
TheoreticalChemistry:itwill,therefore,constituteamajorpartofthisbookseries.
However,thescopeoftheserieswillalsoincludeotherareasoftheoreticalchem-
istry,suchasmathematicalchemistry(whichinvolvestheuseofalgebraandtopol-
ogy in the analysis of molecular structures and reactions), molecular mechanics,
molecular dynamics and chemical thermodynamics, which play an important role
inrationalizingthegeometricandelectronicstructuresofmolecularassembliesand
polymers, clusters and crystals, surface, interface, solvent and solid-state effects,
excited-statedynamics,reactivecollisions,andchemicalreactions.
Recent decades have seen the emergence of a novel approach to scientific
research,basedontheexploitationoffastelectronicdigitalcomputers.Computation
providesamethodofinvestigationwhichtranscendsthetraditionaldivisionbetween
v
vi ProgressinTheoreticalChemistryandPhysics
theoryandexperiment.Computer-assistedsimulationanddesignmayaffordasolu-
tiontocomplexproblemswhichwouldotherwisebeintractabletotheoreticalanaly-
sis,andmayalsoprovideaviablealternativetodifficultorcostlylaboratoryexperi-
ments.ThoughstemmingfromTheoreticalChemistry,ComputationalChemistryis
afieldofresearchinitsownright,whichcanhelptotesttheoreticalpredictionsand
mayalsosuggestimprovedtheories.
The field of theoretical molecular sciences ranges from fundamental physical
questions relevant to the molecular concept, through the statics and dynamics of
isolatedmolecules,aggregatesandmaterials,molecularpropertiesandinteractions,
andtheroleofmoleculesinthebiologicalsciences.Therefore,itinvolvesthephys-
icalbasisforgeometricandelectronicstructure,statesofaggregation,physicaland
chemicaltransformations,thermodynamicandkineticproperties,aswellasunusual
propertiessuchasextremeflexibilityorstrongrelativisticorquantum-fieldeffects,
extreme conditions such as intense radiation fields or interaction with the contin-
uum,andthespecificityofbiochemicalreactions.
Theoretical chemistry has an applied branch – a part of molecular engineering,
which involves the investigation of structure–property relationships aimed at the
design,synthesis,andapplicationofmoleculesandmaterialsendowedwithspecific
functions, now in demand in such areas as molecular electronics, drug design, or
genetic engineering. Relevant properties include conductivity (normal, semi- and
supra-), magnetism (ferro- or ferri-), optoelectronic effects (involving nonlinear
response), photochromism and photoreactivity, radiation and thermal resistance,
molecularrecognitionandinformationprocessing,andbiologicalandpharmaceuti-
calactivities,aswellaspropertiesfavouringself-assemblingmechanismsandcom-
binationpropertiesneededinmultifunctionalsystems.
ProgressinTheoreticalChemistryandPhysicsismadeatdifferentratesinthese
variousresearchfields.Theaimofthisbookseriesistoprovidetimelyandin-depth
coverageofselectedtopicsandbroad-rangingyetdetailedanalysisofcontemporary
theoriesandtheirapplications.Theserieswillbeofprimaryinteresttothosewhose
research is directly concerned with the development and application of theoretical
approachesinthechemicalsciences.Itwillprovideup-to-datereportsontheoretical
methodsforthechemist,thermodynamicistorspectroscopist,theatomic,molecular
orclusterphysicist,andthebiochemistormolecularbiologistwhowishtoemploy
techniques developed in theoretical, mathematical, or computational chemistry in
theirresearchprogrammes.Itisalsointendedtoprovidethegraduatestudentwith
a readily accessible documentation on various branches of theoretical chemistry,
physicalchemistry,andchemicalphysics.
Preface
Thesetwovolumes,whichsharethecommontitleAdvancesintheTheoryofAtomic
andMolecularSystems,containarepresentativeselectionofsomeofthemostout-
standing papers presented at the Thirteenth International Workshop on Quantum
SystemsinChemistryandPhysics(QSCP-XIII).TheQSCP-XIIIworkshop,which
ranfrom6to12July2008,washeldattheimpressivesiteoftheJamesB.Henry
Center for Executive Development of Michigan State University, East Lansing,
Michigan,USA,andwascoordinatedwiththeSixthCongressoftheInternational
SocietyforTheoreticalChemicalPhysics(ISTCP-VI)thattookplaceaweeklaterin
Vancouver,BritishColumbia,Canada.Asamarkoftheclosecollaborationwhich
underpinnedthescientificagendasofbothmeetings,threeofthethirtythreepapers
includedinthepresenttwovolumeshavebeenwrittenbyscientistswhocontributed
inpersonattheISTCP-VICongress.
The QSCP-XIII workshop continued the series that was initiated by Roy
McWeenyinApril1996withameetingheldatSanMiniato,nearPisa,Italy.Held
everyyear,QSCPmeetingsbringtogether,inaninformalatmosphereandwiththe
aimoffosteringcollaboration,chemistsandphysicistswhoshareinterestsinsuch
areasasNovelConceptsandMethodsinQuantumChemistry,MolecularStructure
and Spectroscopy, Atoms and Molecules in Electric and Magnetic Fields, Con-
densed Matter, Complexes and Clusters, Surfaces and Interfaces, Nano-Materials
andMolecularElectronics,ReactiveCollisionsandChemicalReactions,Computa-
tionalChemistry,Physics,andBiology,andBiologicalModeling.Theemphasisof
theQSCPworkshopsisonbroadlydefinedquantum-mechanicalmany-bodymeth-
ods, i.e., the development of innovative theory and its computational realization,
alongwiththeirapplicationtoabroadrangeofscientificproblemsofrelevanceto
chemistry,physics,biochemistry,andrelatedfields.
TheQSCP-XIIIworkshop,whichwasthefirstintheseriesheldinNorthAmer-
ica,wastrulyinternationalinnature.Wewelcomedmorethan100participantsfrom
22 countries from North and South America, Europe, Africa, Asia, and Australia.
The workshop was divided into 19 plenary sessions, during which a total of 64
scientificlecturesweredeliveredinaccordancewiththeusualQSCP“democratic”
allocationofabout30minutesforeachlecture.Theselectureswerecomplemented
bytwo45-minutelongkeynoteplenarytalkswhichfocusedonscienceandrelevant
historicaloverviews,constitutingaspecialsessionthatwasheldon6July,aswellas
byawelcomepresentationbyVicePresidentforResearchandGraduateStudiesat
MichiganStateUniversity,J.IanGray,givenon7July,and36posterpresentations
dividedintotwopostersessions.
vii
viii Preface
Following a tradition of QSCP workshops, the scientific programme of QSCP-
XIII was accompanied by a social programme including a musical concert, a trip
to the Henry Ford Museum in Dearborn, Michigan, and an award ceremony that
tookplaceatthebanquetdinner.Themusicalconcert,coordinatedbyCharlesRug-
gieroofMichiganStateUniversity,wasperformedbyDaniloMezzadriandSusan
Ruggiero-Mezzadri,afluteandsopranoduowhowereaccompaniedbyJudyKabo-
dianatthepiano.Theceremonyoftheawardhonoredfivenomineesandrecipients
of the QSCP Promising Scientist Prize of the Centre de Me´canique Ondulatoire
Applique´e(CMOA).ThefirstPrizewaspresentedtoGarnetK.-L.ChanfromCor-
nellUniversity,USA,andthesecondPrizewassharedbyDavidA.Mazziottifrom
theUniversityofChicago,USA,andA´gnesSzabadosfromEo¨tvo¨sUniversity,Hun-
gary. T. Daniel Crawford from Virginia Tech, USA, and Ste´phane Carniato from
Universite´ Pierre et Marie Curie, France, received certificates of nomination. For
further details of the QSCP-XIII events and programme, including the abstracts
of all lectures and poster presentations, we refer the reader to the workshop web-
pagesat
www.chemistry.msu.edu/qscp13
ThethirtythreepapersintheproceedingsofQSCP-XIIIaredividedbetweenthe
present two volumes in the following manner. The first volume, with the subtitle
Conceptual and Computational Advances in Quantum Chemistry, contains twenty
papersandisdividedintosixparts.Thefirstpartfocusesonhistoricaloverviewsof
significance to the QSCP workshop series and quantum chemistry. The remaining
five parts, entitled “High-Precision Quantum Chemistry,” “Beyond Nonrelativistic
Theory: Relativity and QED,” “Advances in Wave Function Methods,” “Advances
in Density Functional Theory,” and “Advances in Concepts and Models,” address
differentaspectsofquantummechanicsasappliedtoelectronicstructuretheoryand
itsfoundations.Thesecondvolume,withthesubtitleDynamics,Spectroscopy,Clus-
ters,andNanostructures,containstheremainingthirteenpapersandisdividedinto
threeparts:“QuantumDynamicsandSpectroscopy,”“ComplexesandClusters,”and
“NanostructuresandComplexSystems.”
We hope that together the present two volumes, with thirty three authoritative
papersthatareeitheroftheadvancedreviewtypeororiginalresearcharticles,will
provide readers with a good idea of the range of stimulating topics which made
QSCP-XIII such a success. We thank both the contributors to these proceedings,
who sent us their outstanding manuscripts, and the referees, who were willing to
invest time in the unacknowledged effort of reviewing the work submitted. We
greatlyappreciatethehelpandadvicetheygavetoauthorsandeditorsalike.Wealso
thankJeffreyR.Gour,JesseJ.Lutz,andWeiLifortheirassistancewithtechnical
aspectsofthemanuscripts.
WearegratefultotheparticipantsofQSCP-XIII,notonlyforthehighstandard
of the lectures and posters presented at the workshop, which is reflected in these
proceedings, but also for the friendly and constructive atmosphere throughout the
formalandinformalsessions.Thankstotheparticipants,theQSCPworkshopscon-
Preface ix
tinue to provide a unique forum for the presentation and appraisal of new ideas in
thebroadlydefinedareaofquantumsystemsinchemistryandphysics.
WearegratefultotheHonoraryChairsofQSCP-XIIIfortheirsupport,encour-
agement,andadvice.Specifically,wethank(inalphabeticalorder):ErnestR.David-
sonoftheUniversityofWashington,USA,ZohraBenLakhdaroftheUniversityof
Tunis, Tunisia, Raphael D. Levine of the Hebrew University of Jerusalem, Israel
and the University of California, Los Angeles, USA, Rudolph A. Marcus of the
CaliforniaInstituteofTechnology,Pasadena,USA,andRoyMcWeenyoftheUni-
versity of Pisa, Italy. We also express our gratitude to other members of the Inter-
national Scientific Committee of QSCP-XIII, including Vincenzo Aquilanti of the
UniversityofPerugia,Italy,ErkkiJ.Bra¨ndasoftheUniversityofUppsala,Sweden,
LorenzS.CederbaumoftheUniversityofHeidelberg,Germany,SouadLahmarof
the University of Tunis, Tunisia, Aristides Mavridis of the National University of
Athens, Greece, Hiroshi Nakatsuji of the Quantum Chemistry Research Institute,
Kyoto, Japan, Josef Paldus of the University of Waterloo, Canada, Alia Tadjer of
theUniversityofSofia,Bulgaria,CarmelaValdemoroofCSIC,Madrid,Spain,Oleg
VasyutinskiioftheIoffeInstitute,St.Petersburg,Russia,andY.AlexanderWangof
theUniversityofBritishColumbia,Vancouver,Canada,fortheirinvaluablesugges-
tionsandcollectivewisdom.
We thank the Local Organizing Committee of QSCP-XIII, particularly several
members of the Department of Chemistry at Michigan State University, including
ThomasV.Atkinson,ThomasP.Carter,JeffreyR.Gour,JanetK.Haun,andPaulA.
Reed,fortheirdedicationandhardworkatallstagesoftheworkshoppreparation
andorganization,whichresultedinthesmoothrunningofthemeeting.
Finally,noscientificmeetingcanbesuccessfulwithoutsponsors,andQSCP-XIII
wasnodifferentinthisregard.Wearegratefulforthefinancialsupportprovidedto
theorganizersofQSCP-XIIIbyseveralofficesandunitsatMichiganStateUniver-
sity:theOfficeoftheVicePresidentforResearchandGraduateStudies,theOffice
oftheViceProvostforLibraries,Computing,andTechnology,theAT&TLecture-
shipsinInformationTechnologyEndowment,theCollegesofNaturalScienceand
ofEngineering,theOfficeofInternationalStudiesandPrograms,theDepartments
of Chemistry and of Biochemistry and Molecular Biology, and the Quantitative
BiologyInitiative,aswellascorporatesponsors:SGI,JRT,andDell.
It is the editors’ hope that the present two volumes will not only convey the
breadth, depth, and dynamism of the QSCP-XIII workshop itself, but also seed
innovativeideasinthewiderresearchcommunity.
April2009 PiotrPiecuch
JeanMaruani
GerardoDelgado-Barrio
StephenWilson
Contents
PartI QuantumDynamicsandSpectroscopy
QuantumTheoryinTermsofCumulantVariables ..................... 3
YasuteruShigeta,HideakiMiyachi,ToruMatsui,NorisukeYokoyama,
andKimihikoHirao
NonclassicalPhaseSpaceJumpsandOptimalSpawning................ 35
SandyYangandToddJ.Martinez
OntheDifferentialCrossSectionsinComplex-FormingAtom–Diatom
ReactiveCollisions ................................................. 47
PedroBarguen˜oandToma´sGonza´lez-Lezana
Shared Memory Parallelization of the Multiconfiguration
Time-DependentHartreeMethodandApplicationtotheDynamicsand
SpectroscopyoftheProtonatedWaterDimer.......................... 67
MichaelBrill,OriolVendrell,andHans-DieterMeyer
StructuralPropertiesandTorsionalDynamicsofPeroxidesandPersulfides 81
GlaucieteS.Maciel,AnaCarlaP.Bitencourt,MircoRagni,GaiaGrossi,
andVincenzoAquilanti
Theoretical Spectroscopy of Inner-Shell Electronic Processes and
PhotochemistryofFluorescentMolecules .............................103
MasahiroEharaandHiroshiNakatsuji
Electron-β-NuclearSpectroscopyofAtomsandMoleculesandChemical
BondEffectontheβ-DecayParameters...............................125
AlexanderV.Glushkov,OlgaYu.Khetselius,andLudmilaLovett
PartII ComplexesandClusters
QuantumChemicalApproachtoInteratomicDecayRatesinClusters ...155
V.Averbukh,P.Kolorencˇ,K.Gokhberg,andL.S.Cederbaum
xi