Condensation E ff ects on Electron Chiral Asymmetries in the Photoionization of Serine From Free Molecules to Nanoparticles ̌ - Nahon, H

《Condensation E ff ects on Electron Chiral Asymmetries in the Photoionization of Serine From Free Molecules to Nanoparticles ̌ - Nahon, H》由会员上传分享，免费在线阅读，更多相关内容在学术论文-天天文库。

pubs.acs.org/JPCLLetterCondensationEffectsonElectronChiralAsymmetriesinthePhotoionizationofSerine:FromFreeMoleculestoNanoparticlesSebastianHartweg,*GustavoA.Garcia,DusanK.Božanič,andLaurentNahońCiteThis:J.Phys.Chem.Lett.2021,12,2385−2393ReadOnlineACCESSMetrics&MoreArticleRecommendations*sıSupportingInformationABSTRACT:Structuralchangesatthemolecularlevel,occurringattheonsetofcondensation,canbeprobedbyangle-resolvedvalencephotoelectronspectroscopy,whichisinherentlysensitivetotheelectronicstructure.Forlargercondensedsystemslikeaerosolparticles,theobservationofintrinsicangularanisotropiesinphotoemission(βparameters)ischallengingduetothestrongreductionoftheirmagnitudebyelectrontransporteffects.Here,weusealesscommon,moresensitiveobservableintheformofthechiralasymmetryparametertoperformacomparativestudyoftheVUVphotoelectronspectroscopyandphotoelectroncirculardichroism(PECD)betweenpuregasphaseenantiomersoftheaminoacidserineandtheircorrespondinghomochiralnanoparticles.Weobservearelativelylarge(1%)andstronglykineticenergy-dependentasymmetry,discussedintermsoftheemergenceoflocalorderandconformationalchangespotentiallycounterbalancingthelossofangularinformationduetoelectrontransportscattering.ThisdemonstratesthepotentialofPECDasasensitiveprobeofthecondensationeffectsfromthegasphasetobulk-likechiralaerosolparticlessurpassingthepotentialofconventionalphotoemissionobservablessuchasβparameters.13AerosolphotoelectronspectroscopyisanimportanttoolcoreelectronsusingsoftX-rayradiation,wherehigh-energyforthestudyandcharacterizationoftheelectronicphotoelectronsoriginatingfroms-likecore−shellstypicallystructureofparticulatematter,elucidatingpropertiesspecificshowhighphotoemissionanisotropiesthatarestilldetectabletosubmicrometersizedparticles,oftengovernedbysurface13,20evenafterreductionduetoelectrontransportscattering.1−7effects.Furthermore,aerosolphotoelectronspectroscopyForvalenceelectrons,ontheotherhand,condensationeffectscanbeusedasanalternativeandoftenadvantageousapproachontheelectronicorbitalcharacterandtheshort-rangetoobtaininformationonsolidandliquidbulkproperties,suchpotentialwithwhichthephotoelectronsinteractduringthe8,910−12asbulkionizationenergies,solvationeffects,andphotoionizationprocessreducetheβparameterconsiderablyelectrontransportphenomena.13−1721eveninsmallclusterswithoutelectrontransportscattering.DownloadedviaUNIVOFNEWMEXICOonMay15,2021at21:04:28(UTC).Photoelectronangulardistributions(PADs)ofaerosolsInlargercondensedsystemslikelargeclusters,22−25aerosols,16obtainedfromUVandVUVphotoionizationareusuallyandliquidjets,26electrontransportscatteringeffectshaveagovernedbyparticle-specificasymmetries,createdbythestrongeffectontheβparameterswhicharethusfurtherSeehttps://pubs.acs.org/sharingguidelinesforoptionsonhowtolegitimatelysharepublishedarticles.combinationoftheradiation’sfiniteabsorptionlength,lightreduced,becomingoftenvanishinganddifficulttodetect.Thisscattering,andlimitedescapedepthofphotoelectrons,referreddifficultyisfurtherincreasedbythestrongparticle-specific15,18toasshadowingornanofocusing.Theseparticle-sizeandasymmetriesmentionedabove.wavelength-dependentforward/backwardasymmetriesinAnotherkindofasymmetryinthePADs,observedforphotoemission,quantifiedbytheparameterrandomlyorientedfreechiraltargetsphotoionizedbycircularlyα=IIforward/backwarddefinedastheratioofthephotoemissionpolarizedlight(CPL),iscausedbytheso-calledphotoelectronintensitiesintheforwardandbackwarddirections,havebeencirculardichroism(PECD)effect.PECDisanintense(uptoaexploitedtogainadditionalinformationonabroadrangeof14−16,18fewtensofpercent)chiropticaleffectresultinginananoparticles.Intrinsicmolecularphotoemissionaniso-photoelectronforward/backwardasymmetryalongthelighttropiesduetoanonzeroβparameterdescribepreferentialphotoemissioninthedirectionsparallelorperpendiculartothelightpolarizationaxis,duetotheinterferencebetweenReceived:January25,2021outgoingphotoelectronpartialwaves.19Inthevalenceregion,Accepted:February23,2021suchanisotropiescould,ifdetectable,providevaluableinsightsPublished:March4,2021intoelectronicandstructuralpropertiesincomplexsampleenvironments.Sofar,sizableintrinsicphotoemissionaniso-tropiesforaerosolshaveonlybeenreportedfortheemissionof©2021AmericanChemicalSocietyhttps://dx.doi.org/10.1021/acs.jpclett.1c002582385J.Phys.Chem.Lett.2021,12,2385−2393

1TheJournalofPhysicalChemistryLetterspubs.acs.org/JPCLLetter59propagationdirectionthatchangesitssigniftheenantiomerhomochiralityoflife.ThedirectinvolvementofSer8oritshandednessorthelighthelicityisswapped(forreviewsseerefsprotonatedformSerH+asapromoterofchiralamplification827−29).PECDisknowntobeverysensitivetotheelectronic48hasbeendiscussedintheliterature.Insuchacontext,thestructure,i.e.,totheinitialorbitalfromwhichthephoto-studyofSerPECDisofspecialinterestsincethePECDofelectronoriginatesandtothewholemolecularpotentialfromaminoacidshasbeenproposedasaninitialsourceofwhichthedepartingelectronisscatteredoff,i.e.,tomolecularenantiomericexcessalongagivenlineofsightinthe30,3132structuressuchasconformersandisomers.interstellarmedium,whichcouldbelinkedtotheoriginofCondensation-inducedspectroscopiccongestionandelec-life’shomochirality.28,31,60trontransportscatteringeffectsareexpectedtoalsoreducetheThemolecularstructuresofgaseousSerconformershavemagnitudeofthePECDincondensedsystemstoasimilarbeeninvestigatedtheoretically42−44,61andexperimentally.41,45extentastheydoforβparametersinnonchiral(andchiral)Theoreticalresultsforionizationenergieshavebeensystems.SmallclusterPECDstudies33−36showedmajor40,62−644063reported;however,onlyTianetal.andClosePECDchangesuponclustering,demonstratingtheratherreportionizationenergiesformorethanoneconformer.Along-rangemolecularpotentialsensitivityofPECD,butphotoelectronspectrumprovidingexperimentaladiabaticandsurprisinglythedecreaseofthemagnitudeofthePECDisverticalionizationenergieshasbeenreportedbyCanningtonnotalwaysobserved.However,thesystemsstudiedsofarwereandHam.65Tothebestofourknowledgethereexistnorelativelysmall(uptoseveralmonomerunits)sothatphotoionizationstudiesofSerclustersnorofaerosolparticles.extrapolatingtothecondensedphaseisfarfrombeingFurthermore,thepresentPECDstudyforSeraerosolparticlesstraightforward.TheobservationofavalenceshellPECDisthefirstreportonPECDforhomochiralaerosolparticles.effectinlargercondensedsampleslikeaerosolparticleshasnotMassspectraofgasphaseSermoleculesproducedbyaerosolyetbeenreported.Nevertheless,therehavebeenreportsonthermodesorptionwithathermodesorbertemperatureof130theenhancementofthecirculardichroism(CD)ofthetotal37,38°Crecordedforphotonenergiesbetween9.4and12.4eVarephotoionizationyieldinaerosolparticlesofchiralsamples,displayedinFigure1.Allmassspectrashowstrongpeaksatm/ascomparedtotheveryweakCDsignalsinisolatedgasphasez60andm/z75,correspondingtothelossofthecarboxylmolecules.Also,theenhancementofPECDforspatially••group(COOH)andthelossofCH2Oafterprotontransferorientedchiralspeciesinthecaseofanisolatedmoleculehas39fromthe−CH2OHsidechaintotheaminegroup,respectively.beenreportedpreviously.Suchanorientationcanbeseenasafirststepfromrandomlyorientedspeciestowardlocalorder.Potentialenhancementbylocalorderemergingincondensa-tionprocessesmakesPECDhighlyinterestingasaprobetostudytheeffectsofsuchphasetransitionsonchiralbiomolecules.Besides,changestotheconformationalland-scapearealsoexpectedtooccuruponcondensation,whichfurtherincreasesthepotentialofPECD,whichhasbeendemonstratedtobehighlysensitivetomolecularconforma-27,30tions.Suchchangesplayamajorroleincondensation,crystallization,andsolvationofbiologicallyrelevantmoleculeslikeaminoacidsandsugars.TheprerequisitefortheapplicationofPECDtostudycondensationeffectsis,however,thattheintrinsicPECDeffectisstrongenoughorenhancedbythecondensation,inordertooutweightheblurringofangularasymmetriesbyelectrontransportscattering.Inthisexperimentalstudy,carriedoutwithVUVsynchrotronradiationcoupledtoadoubleimagingelectron/ioncoincidencespectrometer(i2PEPICO),wecomparethephotoelectronspectra(PES)andPECDofthechiralproteinogenicaminoacidserine(Ser)inthegasphasewithitshomochiralandracemicaerosolparticles(seetheSIforthecharacterizationofthelatter).Serineisaparticularlyinterestingsystemforseveralreasons.Inthegasphase,thereexistseveralenergeticallylowlyingneutralconformersthatdifferinthearrangementofintramolecularhydrogen40−45bondsthatmightbedistinguishedbytheirPESandmostofalltheirPECDasshownonotherspe-27,28,30,31,46,47cies.Besides,Serisknowntoreadilyformexceptionallystable,thoughnoncovalentlybound,enantiopureoctamerclustersSerandSerH+undervariousexperimental8848−52conditions.TheseoctamerscontainseveralconformersofzwitterionicSermolecules,whilethecrystallineformofsolid53−56Serisbuiltuponasinglezwitterionicconformer.Figure1.MassspectraofgaseousSermoleculesphotoionizedwithFurthermore,Serisassumedtohavebeenamongthefirstphotonenergiesof9.4,10.2,11.0,and12.4eV(bottomtotop).The57,58aminoacidsrecruitedbylifeandisthereforeofsignificantinsetshowstheweaksignalarisingfromintactSercationsofm/z105interestforbiochemicalevolutionandfortheoriginofinthemassspectrumrecordedata9.4eVphotonenergy.2386https://dx.doi.org/10.1021/acs.jpclett.1c00258J.Phys.Chem.Lett.2021,12,2385−2393

2TheJournalofPhysicalChemistryLetterspubs.acs.org/JPCLLetterWhileat9.4eVthosetwofragmentsdominatethemassspectrum,othermassesappearathigherphotonenergies,withm/z87,74,57,and43beingthemostabundant.IntactSerparentcations(m/z105)areonlyobservedinextremelylowabundanceinthemassspectrumrecordedveryclosetotheionizationenergy,at9.4eV,sothatonecaninferthatata130°Csampletemperature(seediscussionofExperimentalMethodsbelow)thiscationishighlyunstable,fragmentingassoonascreatedevenatlowexcessenergy.ThemostabundantfragmentionsaresummarizedinTable1,togetherTable1.MainFragmentMasseswithinthe8.9−12.5eVPhotonEnergyRangeandPossibleDissociationChannelsLeadingtoThoseFragmentsm/zneutralfragmentslostfragmentationprocess87H2OeliminationofH2O60•COOHC−CcleavageαFigure2.Mass-selectedTPESofthemainfragmentsarisingfromthe75•CHOC−Ccleavagewithprotontransferfrom2αβphotoionizationofgasphaseSermolecules(colored)andthesumofOHallfragmentTPES(black).Asmentionedinthetext,theparentsignal74•CHOHC−Ccleavagewithoutprotontransfer2αβistoolow,evenatlowphotonenergies,andthushasnotbeenadded57•CHO+HOC−Ccleavagewithprotontransferfrom22αβtotheplot.SeealsoFigureS4andTableS1forfurtherdataonotherOHfollowedbylossofH2Ominorfragments.43H2OandCO2oreliminationofH2OandCO2orCα−C•COOHandNHcleavagefollowedbylossofNH33Table2.CalculatedAdiabaticIonizationEnergiesandPredictedIonicDissociationChannelsfromReference40withpossibledissociativeionizationpathwaysleadingtotheirFollowingtheLabelingoftheConformersfromReferenceformation.Themassspectraandtheobservedfragmentsagree4041andComparisontotheObservedFragmentsandTheirwellwithpreviousworkonSer,andmostoftheAppearanceEnergiesfromThisWorkfragmentationchannelsobservedfortheSercation(discussedinmoredetailintheSI)havealsobeenobservedforother31,40,46,64,66,67aminoacidsinthepast.40Tianetal.discussthedifferentionicfragmentsandtheirdifferentappearanceenergieswithrespecttothepresenceofthefourmainconformersofSer(displayedschematicallyinFigureS3intheSI),whichdifferintheirintramolecularH-bondarrangementleadingtodifferentdissociativeionizationpathwaysandionizationenergies.Thethresholdphotoelectronspectra(TPES)ofthedifferentfragmentationchannels(seeFigure2)donotjustshowdifferentappearanceenergies(AEs)assummarizedinTable2butalsodifferpronouncedlyinshape,position,andrelativeintensityofthevariouselectronicbands.ThesumTPESwithanionizationenergy(IE)around8.9eVandthreebroadoverlappingbandsagreeswellwiththephotoelectronspectrathethreefragmentationchannels.Atthephotonenergies65describedbyCanningtonandHam.wheremeasurementswereperformedforbothD-andL-Ser,the40Tianetal.havecalculatedadiabaticandverticalionizationPECDdatashowclearly,withinourerrorbars,theexpectedenergiesforthefourmoststableconformersofSer(labeledIa,mirroringbehaviorforthetwoenantiomers.Overall,forany41I′b,IIb,andIIc,followingBlancoetal.)andpredictedgivenorbital(bindingenergy)thePECDexhibitsamarkedpreferredfragmentationchannelsforeachoftheseconformersdependenceonthephotonenergy(PECDisacontinuumbasedonionicequilibriumstructures.Theseresultsareeffect)andonthebindingenergyatanygivenphotonenergysummarizedinTable2andcomparedtotheappearance(PECDisalsoaninitialorbitaleffect),withmaximumvaluesenergiesofthevariousfragmentsinourwork(seetheSIforontheorderof∼4−5%,reachingupto∼9%at10.2eVintheextendedinformationonthefragmentationchannelsandam/z74channel.BecausephotoelectronsejectedfromthesamemoredetailedcomparisonwiththecalculationsbyTianetcationicstateshouldgiveequalPECDindependentlyofthe40al.,includingFiguresS3andS4andTableS1).Thefinalfragmentationpathway,thesignificantdifferencesagreementofthedeterminedappearanceenergies,theshapeofbetweenthePECDmeasuredatagivenbindingenergyfortheTPES,andthepartialagreementofthefragmentationdifferentfragmentmassesfurthersupportsthepreviouspatternsarecompatiblewiththepresenceofthefourmaininterpretationofdifferentconformers,exhibitingacon-conformersunderourexperimentalconditions.former-dependentfragmentationpattern,aneffectalready31Thefragmentmass-resolvedPESandPECDrecordedatencounteredinproline.ThehighsensitivityofPECDonfixedphotonenergiesforthemainfragments,m/z60,75,andmolecularstructureshasbeenpreviouslydemonstra-27,28,30,31,4674,aredisplayedinFigure3.ThesePESconfirmtheted,andthePECDdeterminedfordifferentSerpreviouslydescribedspectraldifferencesamongtheTPESofconformersisanotherexampleforthis.2387https://dx.doi.org/10.1021/acs.jpclett.1c00258J.Phys.Chem.Lett.2021,12,2385−2393

3TheJournalofPhysicalChemistryLetterspubs.acs.org/JPCLLetterFigure4.PESandenergydependentαparametersrecordedathν=9.4,10.2,11.0,and12.5eV(red,blue,green,andblack,respectively)Figure3.PES(toprow)andPECDrecordedforfragmentmassesofforracemicSerparticlesasafunctionoftheelectronbindingenergy.60amu(secondrow),75amu(thirdrow),and74amu(fourthrow)ThePESarescaledtorepresentapproximatelytherelativeatphotonenergiesof10.2eV(leftcolumn),11eV(centercolumn),photoionizationcrosssectionsatthedifferentphotonenergies.Theand12.4eV(rightcolumn).PECDforL-SerisshownbyredinsetshowsarawbackgroundsubtractedVMIimageofracemicSerdownwardpointingtrianglesandforD-Serbyblueupwardpointingparticles(top)recordedat11eVphotonenergyandthetriangles.corresponding2Dcenterslicethroughthereconstructed3Ddistribution(bottom).Thewhitearrowsindicatethelightpropagationdirection.NotethatthesignofthePECD(negativefortheL-enantiomer),forallmasschannels,i.e.,forallconformers,isidenticaltothesignobservedforalanineandprolineforwithitsreconstructedimage,i.e.,thecentersliceofthe28,31,46,60Lyman-αradiation(10.2eV).Thisphotonenergyisreconstructed3Ddistribution.Theenergydependentβofparticularrelevancefortheastrophysicalscenarioregardingparametershavealsobeenobtainedbutarenotshownhere28,60theoriginofthehomochiralityoflife,duetoitslargebecausetheyarevanishing(β≤0.06±0.1)forallofthedominanceintheinterstellarspace.Thefactthatallfragmentsphotoelectronimages.Atallphotonenergies,thePESexhibita(i.e.,allconformers)forwhichweareabletomeasureaPECDsinglebroadbandwithnoresolvedelectronicstructure,unlike28,3160at10.2eVshowthesamesignasprolineandalaninetheisolatedmolecule(seeFigure3).ThePESrecordedatsupportstheproposedscenario,inwhichPECD-induceddifferentphotonenergiesshowallthesameonsetatabout8asymmetricphotoionizationprocessescreatespatialregionseV,roughly1eVbelowthelowestonsetdeterminedforgaswithanenantiomericexcessofaminoacidparentcations.ThephaseSermolecules.Apreviousstudyofaminoacidandcreationofenantiomericexcessis,however,onlypossibleifthepeptidenanoparticlesfoundacomparableshift,albeitslightlyasymmetricallyejectedphotoelectronscanbetranslatedontolarger,betweentheonsetforthenanoparticlesandthegas8therecoilvelocitydistributionofintactparentcations.phase.Theobtainedα-parametersfollowasimilartrendforHowever,coldinterstellarconditionscould,withoutaffectingthefourdifferentphotonenergies.Overthefullwidthathalf-theconformer-independentsignofthePECD,increasethemaximumoftheband,theαparameterstaysratherconstantparentcationyieldbecauseofthestronglyreducedinternalbutdecreaseswithincreasingphotonenergyfrom∼0.73at9.4energyintheneutralmoleculesothatpartoftheparenteVphotonenergy,downto∼0.46foraphotonenergyof12.5cationscouldremainbound,owingtotheshallowbutnoneV.Atlowelectronbindingenergy,i.e.,towardtheedgeofthenegligiblebarriercalculatedforthefragmentationofSerband,theαparametersincreasetowardvaluesaround1,40cations.indicatingavanishingshadowingeffect,correlatedtotheThePESandα-parametersobtainedfromthereconstructionvanishingsignal-to-backgroundfromtheaerosols.ofthephotoelectronimagesrecordedforracemicSeraerosolsIngeneral,aquantitativeinterpretationoftheα-parametersareshowninFigure4onanelectronbindingenergy(eBE)requirespriorknowledgeabouteitherlightscatteringandscale.Notethatallaerosoldatapresentedinthisstudywereabsorptioncoefficients(i.e.,complexrefractiveindices)oftheobtainedforpolydisperseaerosols,welldescribedbylog-materialoraboutthekineticenergydependentelectronnormalsizedistributionswithanaveragemobilitydiameterofscatteringprocesseswithinthematerial.Forexample,prior∼140nm,asdeterminedusingascanningmobilityparticleknowledgeofcomplexrefractiveindexdatacanbeusedtosizer(seeSI).Furthermore,fromtheelectronmicroscopyobtaininformationonelectronscatteringwithinamaterial15,16,18measurementsofthedepositedparticles,theyareassumedtofromtheα-parametersanalysisandviceversa.Thelackbemostlyamorphousinnature,butthepossibilitythattheyofsuchdataforSerinadditiontothepolydispersenatureofmaycontainsomecrystallineregionscannotbeexcluded(seetheatomizeroutputmakesaquantitativeinterpretationofthetheelectronmicroscopyimagesinFigureS2oftheSI).Theobtainedα-parameterscurrentlyimpossible.Afewobserva-insetinFigure4showstherawphotoelectronVMIimagetionscan,however,bequalitativelyrationalized.Theobtainedataphotonenergyof11eVforracemicSer,alongpronouncedtrendtowardlowerαparameters(i.e.,stronger2388https://dx.doi.org/10.1021/acs.jpclett.1c00258J.Phys.Chem.Lett.2021,12,2385−2393

4TheJournalofPhysicalChemistryLetterspubs.acs.org/JPCLLettershadowing)forhigherphotonenergiesagreewithanTheuncorrecteddataisshowntogetherwiththevirtuallyzeroabsorptioncoefficientincreasingwithphotonenergy.SuchPECDbaselinesoftheracemicparticlesinFigureS6oftheSI.anincreaseoftheabsorptioncoefficientisexpecteddirectlyAtallphotonenergies,aclearnonvanishingPECDisobserved,abovetheionizationthresholdofasubstance.ElectronsofascanbeseenfromthenicelymirroringL-SerandD-Serdataidenticalkineticenergyshowthesameelectronscatteringsets.Moreover,theaerosolPECDclearlydiffersqualitativelybehaviorandthereforethesameelectronescapelength.AscanandquantitativelyfromthePECDobservedfortheSergasbeseenfromFigure4,however,inthepresentcasethephaseconformers.Phenomenologically,inthemeasurementsincreaseoftheα-parameteroccursroughlyatidenticalelectronusingphotonenergiesbelow12.5eV,forhighKE(i.e.,lowbindingenergies(i.e.,atdifferentelectronkineticenergies)foreBE)thesignofthenanoparticles’PECDagreeswiththeonealldifferentphotonenergies.ThismeansthattheincreaseinofthegasphaseSer(negativeforL-Ser).TowardlowerKE,thetheαvaluescannotbeattributedtothekineticenergyPECDfirstdecreasestozeroandthenchangestotheoppositedependenceoftheelectronescapelengthbutseemstosignatthelowestKE,aquitespectaculareffectconsideringtheoriginatefromthedecreaseoftheaerosolphotoelectronsignalcorrespondingverybroadandfeaturelessPES.Inthetowardanisotropicbackgroundlevel.Thesameeffectismostmeasurementsata12.5eVphotonenergythesignofthelikelyresponsiblefortheslightincreaseoftheα-parametersPECDappearsinverted,althoughtheverylowmagnitudeandtowardhighelectronbindingenergies,forwhichthesignalrelativelylargeerrorbarsmakeitdifficulttodistinguishthePECDfromzero.intensitiesdecreaseaswell.Itseems,thus,thatthereisnoThechangeofthesignofthePECDisobservedataverypronouncedkineticenergydependenceoftheelectronescapesimilarelectronkineticenergy(∼0.6−0.9eV)(i.e.,largelyprobabilityofphotoelectronsfromsolidSeraerosolparticlesdifferentelectronbindingenergies)forphotonenergiesuptobelow5eVkineticenergy.11eV.IfthissignchangewasrelatedtoafeatureintheThePECDdataobtainedfromthedifferencesbetweentheelectronicbandstructure,itwouldbeexpectedtooccuratLCPandtheRCPimagesforL-andD-SerareshowninFigureidenticalelectronbindingenergies,i.e.,largelydifferent5fordifferentphotonenergies.NotethatthePECDdataiselectronkineticenergies,shiftingby1.6eVbetweenphotoncorrectedforabaselinedeterminedfromracemicSerparticles.energiesof9.4and11eV.Thelackofthispronouncedshiftonthekineticenergyaxisindicatesthatthissignchangecannotbeexplainedbythepresenceofdifferentcongestedelectronic68statesasitisusuallythecaseforgasphaseexperiments,butratherpointsattheeffectofkineticenergy-dependentinteractions,occurringbetweenthedepartingphotoelectronsandthechiralmolecularpotential.Kineticenergyeffectsinthe27,29continuumarewelldocumentedinthegasphaseandarealsoseenhereforthegasphaseSerconformers.Inthecaseofaerosols,anadditionalkineticenergy-dependenteffectarisesfromelasticandinelasticelectrontransportscattering,whichis,however,notexpectedtoaffectthesignofthechiralasymmetry.Inaddition,andcomparedtothegasphase,thelackofdependencyonthebindingenergy(atleastuptophotonenergiesof11eV)isstrikingandmightbeexplainedbythehighlydelocalizedandmixednatureofthe4eVbroadelectronicbandseeninFigure5,duetocondensationeffects.ThissingleinitialstatewouldbeassociatedwithPECDvaluesexhibitingstrongKEeffects,i.e.,continuum(finalstate)effects,suchasasignchangeandmagnitudevariations.Overall,themagnitudeofthePECDisreducedascomparedtothegasphase.WhileforthegasphaseweobservedaPECDofupto>5%,themaximumobservedforaerosolparticles(at10.2eV)isslightlyhigherthan1%.At9.4and11.0eVphotonenergies,thePECDstillreaches∼0.5%,whereasthePECDisevensmaller,barelydistinguishable,at12.5eV.ThereducedmagnitudeofthePECDobservedfortheSeraerosolsascomparedtothegasphasemightbereadilyexplainedbythepresenceofelectrontransportscatteringeffects.Thepossiblemagnitudeofsuchscatteringeffectsonphotoelectronanisotropiesdescribedbyβparametershasbeen1320,21,26previouslydemonstratedforaerosols,liquidjets,and22−25largeclusters.Inpractice,studiesofvalencephotoelectronVMIinfactoftenassumedβparametersofzeroformanykindsofaerosolparticles.TakingthisintoaccountitmayevenbeFigure5.PESandPECDofSeraerosolparticlesrecordedatphotonenergiesof9.4,10.2,11.0,and12.5eVforL-Ser(red)andD-SersurprisingthatthePECDobservedforSeraerosolparticlesis(blue).ThePECDdataiscorrectedaccordingtoeq1,andaPECDonlyreducedmoderately,fromabout2−5%forthegasphasebaselinedeterminedfromracemicSerparticleshasbeensubtractedto0.5−1%foraerosolparticles.Thislimitedreductionmay(seeSI).indicateareducedsensitivityofPECDtoelectrontransport2389https://dx.doi.org/10.1021/acs.jpclett.1c00258J.Phys.Chem.Lett.2021,12,2385−2393

5TheJournalofPhysicalChemistryLetterspubs.acs.org/JPCLLetterscattering.SuchareducedsensitivitycanbeexplainedmeasurementsofgaseousSermoleculesthefocusedbeamofconsideringitsangulardependency.PECDdescribesanaerosolswasalignedontotheheated(130°C)porous66asymmetrydependinglinearlyoncos(θlab)whilethetungstentipofanaerosolthermodesorber(TD)tocreateanisotropydescribedbyaβparameterdependsoncos(2θ)aplumeofneutralgaseousSer,whichwasionizedusingthelabmonochromatizedVUVsynchrotronradiationfromthe(seetheSIfortheformalPECDdefinition).Therefore,PECD71variablepolarizationundulator-basedbeamlineDESIRSatmaybelessaffectedbyelectronscatteringeventsthattypicallySOLEILsynchrotron.Theemittedphotoelectronsandphoto-changetheelectronpropagationdirectiononlybyasmallangleionsaredetectedincoincidenceusingtheDELICIOUSIIIatatime,sincealargeraverageangularchangeisnecessarytodoubleimagingphotoelectronphotoioncoincidencemakethephotoelectronangulardistributionisotropic.270(iPEPICO)spectrometer,whichcombinesaphotoelectronFurthermore,itisverypossiblethattheincreasedlocalorderVMIspectrometerandamodifiedWiley−McLaren3D-inasolidenvironmentenhancestheintrinsicasymmetryviamomentumimagingtime-of-flightphotoionmassspectrometerinteractionsofthedepartingphotoelectronswiththelocallytoperformangle-resolvedphotoelectronspectroscopyonorderedscatteringpotential.Notethatsomeshort-rangelocalmass-selectedsamples.Inthecurrentstudythemassresolutionordercanbeassumedtobepresenteveninamorphoussolids.38isusedtodistinguishdifferentphotoionfragmentationAchiralcrystallattice,ashasbeenreportedfortyrosine,ischannelsandtodiscardbackgroundmolecules,whiletheionnotanecessaryrequirementforsuchanenhancementeffect.imageisfurtherusedtodiscardsignalsarisingfromtheouterAnincreasedintrinsicPECDcreatedbythelocalordercouldregionsoftheplumeofgaseousSerbyexclusivelyusingionsinpartcounterbalancethestrongblurringofanisotropiesfallingwithinaregionofinterestofthepositionsensitiveioncausedbyelectrontransportscatteringprocesses.detector(ROI-filtering).Mass-selectedthresholdphotoelec-Forratherlargeandflexiblemolecules,themoleculartronspectra(TPES)wereobtainedforgaseousL-Serbetweenconformationisaffectedbycondensationaswell,whichinturn8.7and12.5eVandanalyzedfollowingapublishedaffectstheintrinsicPECD,asexperimentallydemonstrated7331procedure.Fixed-photonenergydataacquisitionstoobtainrecentlyongasphaseproline.Indeed,fromFigure3onecanmass-selectedROI-filteredPESandPECDwererunatphotoninferthattheshapeandmagnitudeofthePECDarenottheenergiesof9.4,10.2,11.0,and12.4eV.sameforthedifferentconformersofSerinthegasphase.Forthemeasurementsofdirectaerosolphotoemission,theWhilethestabilityoftheseconformersinthegasphaseisTDwasremovedfromthespectrometerchamberanditsgovernedbyintramolecularhydrogenbonds,itisknownthat,flangereplacedbyanadditionalturbopump.FortheseuponclusterformationorcondensationofSer,someofthesemeasurementsonlythephotoelectronVMIsideoftheintramolecularhydrogenbondsarelostinfavorofspectrometerwasused.ThisnoncoincidentmodeofoperationintermolecularonesandtheneutralSermoleculesaremakesthemeasurementandsubtractionofbackgroundimagestransformedintotheirzwitterionicforms.Inthiscontext,itnecessary.Therefore,backgroundimageswererecordedwhileseemsplausiblethatdifferent,andpossiblyfewer,conformersrunningtheaerosolgenerationwithpurewater.Fixed-photonareinvolvedinthemostlyamorphousparticulatestate.ThisenergyPESandPECDmeasurementswereperformedfortheeffectisalsolikelytoaffecttheenergydependenceandaerosolscreatedfromL-andD-homochiralandracemicSerpossiblyenhancethemagnitudeoftheinitialintrinsicPECDofsolutionsatphotonenergiesof9.4,10.2,11.0,and12.5eV.SeraerosolsascomparedtotheisolatedgasphaseconformersForbothgasphaseandaerosolsmeasurements,thedatawhosenumerousPECDcontributionsmightleadtoablurring46,69acquisitionwascarriedoutforseveralhourswhileswitchingoftheobservedPECD.thelighthelicitybetweentheleft-andtheright-handed(LCPIncontrasttotheanisotropiesdescribedbyβparameters,andRCP)every∼10mininordertolimittheeffectofslowwhichareoftenassumedtobezeroinvalenceshellaerosoldriftsintheexperimentalconditions.Accordingtoapreviouslyphotoelectronimagingstudies,thehighlystructuredand68describedprocedure,thesum(LCP+RCP)anddifferencerelativelylargechiralasymmetrypresentedheredemonstrates(LCP−RCP)imageswereinvertedviathepBasexthepotentialofPECDasanobservablesensitiveto74algorithm,toobtainthePESandPECD(seethedetailsincondensationeffectsfromthegasphasetobulk-likeaerosoltheSI).NotethatPECDisdefinedastwicethedichroicparticles.FuturePECDstudiesofnanoparticlescrystallizinginachirallattice,suchastyrosine,38likelyenhancingchiralparameter,i.e.,2b1,whichrepresentsthemagnitudeofthenormalizedforward/backwardasymmetryinthedifferenceasymmetries,wouldallowinadditiontheexplorationofimage(seetheSIfordetails),andisreportedasapercentagesupramolecularchiralityeffects.ofthetotalphotoionizationcrosssection.SincetheDESIRSbeamlinedoesnotprovideexactlyidenticalphotonfluxesfor■EXPERIMENTALMETHODSLCPandRCPlight,theimageswerenormalizedtothesameTheexperimentalsetupandmethodologyusedforthecurrenttotalelectroncountbeforeimagesubtractionandsummation.16,66,68,70−72Fortheshadowedaerosolphotoelectronimages,itisshowninstudyhavebeenpreviouslydescribedindetail.Briefly,themeasurementsofisolatedSermoleculesweretheSIthatanidenticalmethodologycanbeusedtoextracttheperformedonSermoleculesbroughtintothegasphasebyPECD,althoughtheanisotropiescreatedbytheshadowing31,46,66effectareconvolutedwiththePECD.Onlyacorrectiongivenaerosolthermodesorption,asoftvaporizationmethod,welladaptedtofragilebiomoleculeswithlowvaporpressures.byAnatomizer(TSI,model3076),operatedwith0.5−1.5barof2He,anddiffusiondriers(TSI,model3062)wereusedtocreate(1+α)aerosolsfromaqueoussolutionsofSer(1g/L).ThesePECDcorrect≈PECDobserved4α(1)aerosols,withanaveragemobilitydiameterofabout140nm(seeSI),weretransmittedintoavacuumandfocusedintotheneedstobeapplied,tocorrectforthenormalization16ionizationregionviaanaerodynamiclenssystem.Fortheprocedure.2390https://dx.doi.org/10.1021/acs.jpclett.1c00258J.Phys.Chem.Lett.2021,12,2385−2393

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