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Theory of time- and frequency-gated spontaneous emission from systems with nonadiabatic coupling and dissipation [Elektronische Ressource] / Andrei Pisliakov

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dieInstitutDomcf?rnat.)PheiysikGradesaliscT?rlerheLaubundM?ncTheoretiscdesheNaturwissenscChemie,orsitzender:Lehrstuhl1.f?rUniv.-Prof.TheoretiscwurdehehniscChemietderChemieTademiscecDoktorshnisc(Dr.henDissertation.UnivDr.ersit?tderM?ncDr.heneTheoryh.c.ofDietime-8.10.2003andTfrequency-gatedUnivspeingereicondurctaneousakult?temission4.11.2003fromaksystemshenwitheinesnonadiabaticdercouplinghaftenandrer.dissipationgenehmigtenAndreiVPisliakUniv.-Prof.oA.vPr?ferVDissertation:ollst?ndigerUniv.-Prof.AbW.druckk2.derDr.vA.onerauderDissertationFamakult?tbf?rderChemieecderhenTersit?techenhnischhenundUnivhersit?tFM?ncf?rhenamzurangenommen.Erlangung.Con.ten.ts.1.In.tro.duction.1.23.4Time-.and36frequency-gated.sp.on.taneous3.2.2emission:.general.theory.7.2.1.In.tro.duction..4.2.40.4.2.2.....resp.....wnian...3.3.1.......................transfer...............25....7.2.2.Denition.of.the.time-resolvresolutioned.sp.ectrum........functions.....eects...............Analytic....9342.3.P.olarization..3.5.........uorescence.In.........del...............(Redeld...42.Harmonic...............3.2.1.functions..11.2.3.1.Denition....and.........3.3.................resp...........3.3.2...............oscillator11.2.3.2.Calculation.of.the.p.olarization:.p33erturbativonsee.approac.h......Memory....13.2.3.3.Time-.and.frequency-resolv.ed.signal.in.terms.of.resp.onse.functions.15.2.3.4Time-resolvCalculationultrafastof39respductiononse.functions..............transfer...............Hamiltonians....16.2.4.

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Published 01 January 2003
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dieInstitutDomcf?rnat.)PheiysikGradesaliscT?rlerheLaubundM?ncTheoretiscdesheNaturwissenscChemie,orsitzender:Lehrstuhl1.f?rUniv.-Prof.TheoretiscwurdehehniscChemietderChemieTademiscecDoktorshnisc(Dr.henDissertation.UnivDr.ersit?tderM?ncDr.heneTheoryh.c.ofDietime-8.10.2003andTfrequency-gatedUnivspeingereicondurctaneousakult?temission4.11.2003fromaksystemshenwitheinesnonadiabaticdercouplinghaftenandrer.dissipationgenehmigtenAndreiVPisliakUniv.-Prof.oA.vPr?ferVDissertation:ollst?ndigerUniv.-Prof.AbW.druckk2.derDr.vA.onerauderDissertationFamakult?tbf?rderChemieecderhenTersit?techenhnischhenundUnivhersit?tFM?ncf?rhenamzurangenommen.Erlangung.Con.ten.ts.1.In.tro.duction.1.23.4Time-.and36frequency-gated.sp.on.taneous3.2.2emission:.general.theory.7.2.1.In.tro.duction..4.2.40.4.2.2.....resp.....wnian...3.3.1.......................transfer...............25....7.2.2.Denition.of.the.time-resolvresolutioned.sp.ectrum........functions.....eects...............Analytic....9342.3.P.olarization..3.5.........uorescence.In.........del...............(Redeld...42.Harmonic...............3.2.1.functions..11.2.3.1.Denition....and.........3.3.................resp...........3.3.2...............oscillator11.2.3.2.Calculation.of.the.p.olarization:.p33erturbativonsee.approac.h......Memory....13.2.3.3.Time-.and.frequency-resolv.ed.signal.in.terms.of.resp.onse.functions.15.2.3.4Time-resolvCalculationultrafastof39respductiononse.functions..............transfer...............Hamiltonians....16.2.4.Do.orw.a.y-windoofw.represen.tation.of.time-resolv.ed3.2sposcillatorectra.................17.2.4.1.Do.orw.a.y-windo26wAnalyticpicture:onseop.erator.form................27.Time.frequency.eects....17.2.4.2.Do.orw.a.y-windo28wBropicture:oscillatorcomputational.asp.ects...................19.2.4.3.Connection30bAnalyticetonsew.een.the.t.w.o.theoretical.approac.hes....30.Dissipation........20.2.4.4.T.ransien.t.eects........31.Drude.................................3.4.1.resp.functions......21.2.5.Do.orw.a.y-windo.w.picture3.4.2foreectsdissipativ.e.systems......................34.Summary..21.2.6.Summary............................4.ed.of.electron.systems.4.1.tro............................23.3.Time-resolv39edElectronuorescencemoof.simple.mo.del.systems.25.3.1.In.tro.duction..........4.2.1.............................40.Equations.motion.theory)...............iii.‚=774
.Sp.ecic.examplesBibliographandSummarydiscussion......P.......6.5.2.Wigner.....with.......6.2...taneous.Applications.Bro...7.C43.4.3.1InIn.tegral5.3.5signal....mo.......del.........Analytic...phenomenological.........systems.....on.treatmen.of..........43.4.3.2.Electronicspcoherence.in.electrondeltransfer..emen...............6.tro......44.4.3.3.Vibrational.coherence.in.electron.transferresp...and.framew.......del.....6.5.1.del...theory47Summary4.3.4.Time-.and.frequency-gated.spTime-onectrataneousBemissionexcitationspinectraation........49.4.3.562Finitesignalpump.duration............ed.........5.3.6.single-excited-state.....66.impro.of...........67..52.4.4.Summary............relaxation.6.1...................mo.................69.for.functions.....6.4.sp.in.of53mo5.Application:.time-resolv.ed.uorescence74ofthethe.TCNE-HMB.complex.55.5.1.In.trowithductionoscillator.......with.electron.78...................85.frequency-gated.emission.terms.ectrograms.erturbativ.of.cess.e.framew.phenomenological.del.97..........55.5.1.1.Exp.erimen.ts..5.3.4.tegral.............................64.Time-resolv.uorescence.ectrum...............66.Comparison55the5.1.2moPrevious.sim.ulations.and.theoretical.in5.4terpretationsossible.v.ts.the.del......56.5.1.3.Our.goals........5.5...................................68.Phenomenological.mo.69.In.duction......57.5.2.Computational.details....................69.The.del..............................58.5.3.Results6.3andexpressionsinnonlinearterpretationsonse...........72.Time-.frequency-gated.on.emission.the.ork.the.relaxation.del...................6.559of5.3.1moCut.at.4.3.CONTENTS.iv....nm............76.Comparison.a.wnian.mo...........77.Comparison.Redeld.for.transfer...6.6......59.5.3.2.P.eak-shift......................83.Conclusions.A.and.sp.taneous.sp.in.of.sp.89.Nonp.e.t.the.pro.91.Pump-prob.signal.the60ork5.3.3theComparisonrelax-ofmosev95eralycuts.system-bathListwofECabbreviationsetSE--dospvonytaneousdensitemissionCTFvGa-wtime-pacand-frequency-gatedSBCF--matrixcorrelationtransferfunctionvibrationalRFelectronic--resporwonsey-windofunctionWP-TLSa-etkwDMo-levdensitelmatrixsystem-RRDMWreducedAy-ETrotating-welectronaVv-ecoherenceappro-ximationcoherenceDWandTdaughteromymywifetallyChaptercal1excitedInossiblytrobductiontheSpTheectroscopictributemeasuremenotsortunitarepump-probcondelavsuccessfullyencontionallystim-ptial,erformedspeitherininofthecoher-timeh-oruorescence.inthetheandfrequencyhniquedomain.isThethet,wItoulatedkindssignal,ofpulses.exptributionerimenatsvcanyhoMukwproevtheerorderbshouldepsuccessfullyycomspbined,protherebtheyetalloItswingtransienushniquetolongfolloinwthethemantimepump-probevresonanceolutionandofortancespexcited-stateectradynamics)[13].vWiththenopumpwoneadaandyseatricveailableerviewfstecpulsessp[4,see5],okv[1].arioustectime-resolvanedtospolutionectroscopicButtecmonitorhniquesdynamics,enabletheusdealingtonamelyobservspetime-resolvthepump-probevyolutionresolutionofbspendenceectraonintimerealeentime,eandtecthisusabsorptiontoThismonitorbmicroscopicfornWhuclearinmotiontecandistheterpretationmostbelemenprotarytoprosignal,cessesulatedofand,cexcited-statehemicalbleacdynamicsofwhicbhemissiontakande(reectingplacecessesontheultrafastpump-probtimeenscalesof[610].vInprobparticular,avexpariousthetime-resolvstateedthetec(withouthniquestecha1vcomprehensivetheoreticalbveenofappliedarioustohniquesstudyultrafastdirectlyectroscopthe,prothecessesoofofultrafastamelelectronSometransfer,theseprotonhniquestransfer,videsolvoppationydynamicsstudyofevdivoferseences.materialinsystems,torangingthefromstatediatomicsonetousebiomoleculestec[11].niquesThewithbasicopulations,idea,ofetime-resolvectroscopedandspedectroscopInyeisectroscopto,observtimeeisthevidedevyolutiondepofofthesignalsptheectrumy(and,btherefore,wthepumpsystemprobunderpulses.study)commononhni-therealizationultrafastthetimescale.tIntectime-[1216].resolvtecedhasspeenectroscopusedya,time.thereyexistoneaterestednotherumhniques?bproblemerinofintecofhniquesresults,(e.g.,ecausephotonyeccessesho,tributepump-theprobee,namelytime-resolvstimedemission,uorescence,Raman,vparious,four-wabsorption,aso-calledvhing.eismixingimptecthathniques),othwhiculatedh(reectingmainlydynamics)dierstiminRamantheground-statenproumconbtoerooferalllaserepulsesevused,inthecasespsequenecicnon-oproperlappingertiesandofetheAslaserconsequence,elds,cannotanderimentheseparatewgroundaexcitedyconoftodetectionpump-probofsignaltheusingspecialectroscopichnicalsignals.ks).Forthe2GCHAPTERderiv1.etINTRTFODUCTIONelectronicOnathe(CFotherdynamicshand,ethedevfemTFtosecondlasertime-resolvtheedlikuorescencegenerallysignalClearlyconsistscomplicatedsolelyexpofcasetheoruorescencedescription(excitedtasksstate)ccomper,onenultrafastt.canSomeasuredthisresults.tecopulationhniquetime-dephassignalanorimpareortandetectiontinadvandanmicroscopictagemoothroughvwhicerofdivt,ersesystems,pump-probteracteeloptecsignalhniques,lter.sinceend,thecomplicatedsignalparameters.isex-considerablythereforeeasiertitativtomaterialinaterpret.andThecal-presenendentvthesiserimenists.devmeasuredotedptohthewhicdeverimenelopmenthetinuencedofus,theittheorytheofintimetheandsignalsfre-presenquencyforgatedand(TF(ET)G)wspofonlimitedtaneousTherefore,emissionw(SE)aspframewectroscopSEyde(whiccouplingshbath.isws:anothereigenstate-free,nametoforatheortime-resolvmeasurededsignalsuorescencewspaectroscopony).andTheinrstGexperimenerimentaltalhoobservextractationinformationofofcoherenfromtTherewgapaeenverimene-pacpreferkquanetthe(WP)electronicdynamicsyviacorrelationthewhileTFmeasureGtSEittecthathniqueGwtheasdynamics.repis,ortedopulationinand[17]extenforthethetransiensoconnecteddiumpdimerare(seeyalsocess.refs.systems[1820]).ultrafastLaternecessaryon,ducecoherenoftproeectstheinestablishTFofGtallySEtherespInonsesthesis,hathisverale(Chapterbforeenultrafastmeasured(ChaptersforWdivterseasystems,Grangingisfromadiatomicmaterial-systemmoleculesultimatetopresenpisolytatomicvdonor-acceptororiencomplexesfor[13,TF7,non1722].mBywithmonitoringter-thehSE,aonespgetsasthetooppunivortunitofySE,tothekineepmonotrachromatorkfrequencyofThevibrationalTFWPSEdynamicsdepinhotheevelectronicallyinexcitedquitestatemannerasthewpulseellsystemasWhendecaterpretingyTFofSEthepexcitedts,state.fundamenThequestionTFarises:GwSEonehasquanbeecomeonandynamicseectivtheesystemtotheolsignals?foristhecertainmonitoringbofwthetheoreticalexcited-stateexpdynamicstalofTheoristsvtoariousculatesystemstitiesrangingefromtime-depiso-tlatedpdiatomicprobabilitmoleculesortoariousratherfunctionscomplexs),systemsexp(carotenoids,talistsccertainhromophore-solvendenentransientIndeed,systems,ispassumedorphtheyrins,TForSEphotoactivmapseexcited-stateyopulationelloButwquestionprotein)whic[7,p17,(diabatic2328].adiabatic)Thetotechhnicalt?realization,ofexpTFtalGtsSEindirectlyspwithectroscopelectronicyopulationisandthestronglyuorescencebup-conthevproersionThtecforhniquewith[2933],andindynamics,whicishtothetroSEexplicitlyanddescriptionatheshortGup-concedurevtoersiontheory(ortotimerigorouslygate)connectionpulsetheareerimenmixedmeasuredinwithaunderlyingnonlineardynamics.crystal,theandtthewinstudytegratedissueinsevtensitsimpleydelsof3)themainlysumthefrequencyofiselectron-transfermonitored.systemsThe4time6).resolutioneisanactohieveedtheorybTFecauseSEthehgatenotpulsetocreatesparticularasimpletimedynamics.windothewgoalfortheSEtandorkthethesignalelopmendepofendscononenienthecomputationallytimeteddelaorkythebofetGwofeentrivialthee.g.,excitationulti-mopulsesystemsandstrongaintimestatewindowhicw,inandwiththethermalfrequencyTheresolutionecicisareacfollohiev(i)eddevbayersal,dispdescriptionersingthetheGup-(ii)conclarifyverted