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heanomalous N-dependenceofthe S2lifetimesandpredictedlocationofthe1B !ustatewithinthe S2ÐS1gapinitiatedanumberofexperimentalstudiessearching forspectralsignaturesofthe1B !ustate.2.1.Transientabsorptiondata TheÞrstassignmentoftransientabsorptionfeaturestothe1B !ustatewasreportedbyZhangetal. [25]whoassignedbandsinthe near-IRregion(800Ð950nm)ofneurosporeneasduetoatransi- tionfromthe1B !ustate.ItwasconcludedthattheabsorbingS 2statedecayedinlessthan70fstothe1B !ustatethatfurtherde- cayedtotheS 1statewithin190Ð260fs,dependingonsolvent.This sequentialschemewasfurtherextendedalsotoothercarotenoids withN=9Ð13 [26]andevensupportedbyßuorescenceup-conver- siondatafromthesamegroup [27].Asomewhatsimilarrelaxation schemewasproposedbyCerulloetal. [28]whoused15fspulses tostudyexcited-stateprocessesin b-carotene.Theseauthorsalso assignedthetransientabsorptionfeatureinthenear-IRtoatran- sitionoriginatingfromanintermediatestatedenotedS x.Their argumentwasbasedonobservationofthepreviouslyunknown transientabsorptionbandcenteredaround800nm.Theyassigned the800nmbandtothe1B #ustatethatdecayedwithin "10fsto formthecharacteristicnear-IRfeaturepeakingat1000nmthat wasattributedtotheS xstatethattheauthorsidentiÞedasthe 1B!ustate.ThemodelinvolvingtheS xstatewasfurtherextended toaseriesofcarotenoidswithdifferentconjugationlengths [29].Althoughthismodel(denotedasScheme1in Fig.3 )offereda reasonableexplanationoftheanomalous N-dependenceoftheS 2lifetimes,italsohadaseriousproblem.Itassumedthattheorigin oftheÔS 2emissionÕisnottheS 2state,butthe1B !ustate,because theassigned1B !ulifetimesmatchedthoseobtainedfromßuores- cenceup-conversionexperiments.Thisassignmentoftheemission originwouldrequirethatthetransitionbetweenthe1B !ustateand thegroundstate,whichisforbiddenintheC 2hpointgroup 2Effectiveconjugationlengthofacarotenoidwithvariousfunctionalgroupsis estimatedonthebasisofcomparisonofitsS 1lifetimewiththelifetimesof carotenoidswithlinearconjugatedchain.e.g. b-Carotenehastheeffectiveconjuga- tionlength10,becauseitsS 1lifetimeiscomparablewiththelinearcarotenoid spheroidenethathas10conjugateddoublebonds. Fig.2. Dependenceofenergiesofcarotenoidexcitedstatesonconjugationlength. TheenergiesoftheS 1state(opencircles)wereobtainedfromS 1ÐS2spectra[5],the energiesofthe1B !uarebasedonresonanceRamanproÞles [7],andenergiesofthe S2andA #gstatesareobtainedfromabsorptionspectra.Thedottedarrowsdenote expectedenergiesofthe1B !uÑ1A#gtransitionfor N=9and13. 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"#$!% $EI!!5+/A'1>-&!"##K!L.*'1)32!5-*.1)3;!%+)1*&A$9 !featuresofthecomplexwithitsspectroscopicpropertiesand attemptingtorationalizeitsexceptionallyhighefficiencyof energytransferbetweenperidininandChl a.14-30Thephotochemicalbehaviorofcarotenoidsandlong-chain polyenesisdominatedbythepropertiesofthetwolowest-lying excitedsingletstates.Becausethepropertiesofthesestatesin low-symmetry,highlysubstitutedpolyenescanbeunderstood byreferencetothecorrespondingstatesobservedunderrigorous C2hsymmetry,itiscommontousethe C2hsymmetrylabelsfor reference.31-33Thelowestexcitedsingletstateinlong-chain linearpolyenes,S 1,has 1Ag*--likesymmetryandisoptically forbiddenunderone-photonselectionrulesbecausetheclosed shellgroundstatehasidenticalsymmetry.Thesecondexcited singletstateinthesepolyenes,S 2,has 1Bu*+-likesymmetryand isstronglyallowedunderone-photonselectionrules.Thisstate isresponsibleforthestrong !maxabsorptionbandobservedin carotenoids.ThesuperscriptÒ +ÓandÒ-Ólabelsrefertothe configurationalpropertiesofthestateswithreferencetothe additionorsubtractionofcomponentexcitations. 34Minusstates, suchasthe 1Ag*-state,aredescribedtoafirstapproximation intermsofthesubtractionoftwoone-electronexcitations. MinusstatesareÒcovalentÓincharacter,areferencetoavalence bonddescriptioninvolvingalinearcombinationofbonding structuresthathavesmallamountsofchargeseparation.In contrast,Ò +Óstatesareionicincharacterandaredescribedto afirstapproximationintermsoftheadditionoftwoone-electron excitations.Thus,Ò +Óstatesareoftenintensebecauseofthe additivepropertiesoftheparticipatingconfigurations.Ionic statesaretypicallystabilizedbyapolarenvironment,whereas covalentstatesarerelativelyunaffectedbythepolarityofthe polyenechainorenvironment. 35Inmanyrespects,theproperties oftheexcitedstatesaredeterminedmorebytheÒionicÓ( +)versusÒcovalentÓ( -)propertiesthanthesymmetric(g)versus unsymmetric(u)labels.Thepositionsanddipolarpropertiesof boththe 1Ag*--likeand 1Bu*+-likestatesareimportantbecause theabsorptionpropertiesaretypicallydominatedbyS 2,whereas thephotochemicalpropertiesaredominatedbyS 1.36Thechallengeistoassigntheenergeticanddipolarpropertiesof theS 1state,becauseitisopticallyforbidden.Althoughthisstate canoftenbeobservedinfluorescence,andtheproperties deducedfromananalysisofthefluorescencelifetimeand emissionprofile,theemissiontakesplacefromarelaxed excited-stategeometry.TheFranck -Condonpropertiesofthe S1statearethereforenotwell-established,anditisoftennot possibletoassignthelocationofthesystemorigin.Finally, recentinvestigationshavesuggestedthatlongerpolyenesand carotenoidspossessotherelectronicstates,e.g.,a 1Bu*--likestate,betweenS 2(11Bu*+)andS 1(21Ag*-).37-40One-photonandtwo-photonabsorptioninto 1Bu*-statesisparityforbidden, andinlinearpolyenes,the 1Bu*-stateisspectroscopicallysilent inbothoneandtwophotonspectroscopy.BirgeandPiercehave shown,however,thatthisstatebecomestwo-photonallowed whentherearecis-linkagesorpolargroupsinthepolyene chain.34Peridininisahighlysubstitutedcarotenoidassociatedwith thePeridinialesgroupofdinoflagellates. 41-43Asshownabove, themoleculedisplaysanatypicalC 37carbonskeletonfor carotenoidsandpossessesanallenegroupandalactoneringin conjugationwiththe "-electronconjugatedsystem. 44Wehave labeledthecarbonatomsalongthepolyenechainusinga simplifiednumberingschemetofacilitatediscussionofthe conformers.Notethatthecarbonylgroupofthelactoneringis alsopartofthepolyeneconjugatednetwork.Thesefeatures,in additiontoepoxyandacetatefunctionalgroupsubstitutions, suggestnosymmetryatall.Yet,thesteady-stateabsorptionand fluorescencespectraofperidinininnonpolarsolventsarevery similartothoseusuallyobservedincarotenoids.Peridininhas astrongabsorptionbandinthevisibleregionthatshiftstolower energywithincreasingsolventpolarizability. 29Thisbehavior identifiesthisbandwiththestrongdipole-allowed 1Ag*-f1Bu*+-liketransition.Thefluorescencespectrumofperidinin issignificantlyred-shiftedfromitsabsorptionspectrumindicat- ingthattheemissionoriginatesfromalower-lyingsingletstate, whichisconsistentwitha 1Ag*--likestate. 29,45Thisobservation istypicalofcarotenoidsandpolyeneshavingmorethanthree butlessthanninecarbon -carbondoublebonds. 46Thedynamics oftheS 1stateandtheS 1fSntransientabsorptionspectrum ofperidininarenottypicalofcarotenoids,however.Peridinin exhibitsapronouncedsolventdependenceofitsS 1fSnFigure1. Structureofthepigmentsassociatedwithone-thirdofthe trimericminimalunitcomprisingthePCPcomplexisshowninAbased onPDBentry1PPR(Hofmann,E.;Wrench,P.M.;Sharples,F.P.; Hiller,R.G.;Welte,W.;Diederichs,K. Science1996,272,1788).The peridininmoleculesarecoloredtoreflectthepseudo2-foldaxisthat runsverticallythroughthecenteroftheprotein.Theperidininmolecules transferenergytotheChl- amoleculesshowninlightgreen.InsertB showsthestructuresofalloftheperidininmoleculesorientedfor maximaloverlapinthepolyenechain.Amedianstructureofthe peridininmoleculeswithinthecrystalisshowninCandcomparedto thelowest-energyvacuumstructurebasedondensityfunctionalmethods [B3LYP/6-31G(d)]inD. PhotochemicalPropertiesofPeridinin J.Phys.Chem.A,Vol.107,No.40,2003 8053!"#!$%&'()*!&+',-,./',&%!&0!1'*23'2*)!,%!454!'(/'!,1!'(&26('!'&!)%(/%3)!'()!7,)8 9!&0! '()!: #;1'/')!)%)*67 ;'*/%10)*!3(/%%)8!'&!'()!< 7!1'/')!&0!5(8 !!!3&-)1!0*&-!3(/%6)1!,%! 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theisomerizationreactioncoordinate(process1ofChart3a)is followedbyaninternalconversionS 1fS0fromtheperpen- dicularminimum 41(process2ofChart3a).Themonoexponen- tialdecaymeasuredatlongwavelengthhasbeenattributedto thisinternalconversion.Incomparisonwiththeultrafast disappearanceoftheexcitedpopulationinbacteriorhodopsin 11(500fs),theinternalconversionS 1fS0in1144-Cis significantlyslower(4.5 -12ps).Thisslowprocess,inturn, allowsthedetectionoftherisetimeofthefluorescence. Thecomputedpotentialenergysurfacetopologyinthe FCregioncoupledwiththeresultswithabinitiosemiclassical dynamicscomputationsneartheregionoftheTICTminimum providesa tentatiVerationalizationfortheseexperimentalresults. WehavedemonstratedthatthefirstrelaxationprocessonS 1isbarrierless(seeChart2AandFigures2and3)andcorresponds toskeletalstretchingcoupledwithtorsion.Thisfeaturecanbe relatedtothefluorescencedecay atshortdetectionwa Velengths(regionclosetothe FC).Thus,apartofthepopulationremains neartheFCregionlongenoughtobeobserved.Fromourresults itisclearthatthereactionpathtotheTICTminimumbreaks symmetrytwice,soonemayhaveaslowIVRwithconsequent increasedlifetimeinthehigh-energyregion.Wecanspeculate Figure8. S1andS 0probabilitiesinthehoppingregionofthetrajectory. Chart3 UltrafastRadiationlessDeacti VationofOrganicDyesJ.Am.Chem.Soc.,Vol.122,No.12,2000 2921theisomerizationreactioncoordinate(process1ofChart3a)is followedbyaninternalconversionS 1fS0fromtheperpen- dicularminimum 41(process2ofChart3a).Themonoexponen- tialdecaymeasuredatlongwavelengthhasbeenattributedto thisinternalconversion.Incomparisonwiththeultrafast disappearanceoftheexcitedpopulationinbacteriorhodopsin 11(500fs),theinternalconversionS 1fS0in1144-Cis significantlyslower(4.5 -12ps).Thisslowprocess,inturn, allowsthedetectionoftherisetimeofthefluorescence. Thecomputedpotentialenergysurfacetopologyinthe FCregioncoupledwiththeresultswithabinitiosemiclassical dynamicscomputationsneartheregionoftheTICTminimum providesa tentatiVerationalizationfortheseexperimentalresults. WehavedemonstratedthatthefirstrelaxationprocessonS 1isbarrierless(seeChart2AandFigures2and3)andcorresponds toskeletalstretchingcoupledwithtorsion.Thisfeaturecanbe relatedtothefluorescencedecay atshortdetectionwa Velengths(regionclosetothe FC).Thus,apartofthepopulationremains neartheFCregionlongenoughtobeobserved.Fromourresults itisclearthatthereactionpathtotheTICTminimumbreaks symmetrytwice,soonemayhaveaslowIVRwithconsequent increasedlifetimeinthehigh-energyregion.Wecanspeculate Figure8. S1andS 0probabilitiesinthehoppingregionofthetrajectory. 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