Rydberg-states-of-chloroform-studied-by-VUV-photoabsorption-spectroscopy

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RydbergstatesofchloroformstudiedbyVUVphotoabsorptionspectroscopy

ParamJeetSingh,AparnaShastrin,R.D’Souza,B.N.JagatapAtomicandMolecularPhysicsDivision,BhabhaAtomicResearchCentre,Trombay,Mumbai400085,India

articleinfoArticlehistory:Received15April2013Receivedinrevisedform11June2013Accepted14June2013Availableonline21June2013Keywords:ChloroformVacuumultravioletPhotoabsorptionRydbergseriesVibronicbandsSynchrotronradiationabstractTheVUVphotoabsorptionspectraofCHCl3andCDCl3intheenergyregion6.2–11.8eV(50,000–95,000cm−1)havebeeninvestigatedusingsynchrotronradiationfromtheIndus-1source.Rydbergseriesconvergingtothefirstfourionizationlimitsat11.48,11.91,12.01and12.85eVcorrespondingtoexcitationfromthe1a2,4a1,4e,3e,orbitalsofCHCl3respectivelyareidentifiedandanalyzed.Quantumdefectvaluesareobservedtobeconsistentwithexcitationfromthechlorinelonepairorbitals.Vibrationalprogressionsobservedintheregionof72,500–76,500cm−1havebeenreassignedtoν3andcombina-tionmodesofν3+ν6belongingtothe1a2

-4ptransitionincontrasttoearlierstudies

wheretheywereassignedtoaν3progressionsuperimposedonthe3e-4pRydbergtransition.TheassignmentsarefurtherconfirmedbasedonisotopicsubstitutionstudiesonCDCl3whoseVUVphotoabsorptionspectrumisreportedhereforthefirsttime.Thefrequenciesoftheν3andν6modesinthe4pRydbergstateofCHCl3(CDCl3)areproposedtobe󰀁454(409)cm−1and󰀁130(129)cm−1respectivelybasedonthevibronicanalysis.DFTcalculationsofneutralandionicgroundstatevibrationalfrequenciessupportthevibronicanalysis.ExperimentalspectrumisfoundtobeingoodagreementwiththatpredictedbyTDDFTcalculations.ThisworkpresentsaconsolidatedanalysisoftheVUVphotoabsorptionspectrumofchloroform.&2013ElsevierLtd.Allrightsreserved.

1.IntroductionChlorinatedorganiccompoundsareextensivelyusedinindustriesandrankamongstthemajorenvironmentalpollutants.Vacuumultraviolet(VUV)photoabsorptionstu-diesofchloromethanesareimportantforunderstandingatmosphericandinterstellarchemicalprocessesinvolvingproductionofatomicchlorineandchlorinecompounds.Chloroform,whichisemittedintotheEarth'satmospherefrombothnaturalandanthropogenicsources,isofspecialrelevancetotroposphericchemistry,althoughitscontribu-tiontostratosphericozonedepletionisnegligibleduetoitsshortlifetime[1].OwingtotheweakC–Clbond,CHCl3isanidealcandidateforstudyofinternaldissociationdynamicsanditsUVphotolysishasbeenstudiedexten-sivelyinthelaboratoryfromafundamentalpointofview[1]andreferencestherein.Incontrast,VUVphotoabsorp-tionstudiesofchloroformarerelativelysparseandfewinnumber[1–7],oftenbeinglimitedto193nmphotolysisstudies[1,7].Thevacuumultravioletabsorptionspectrumofchloro-formwasfirstreportedbyZobelandDuncanin1955[2].Subsequently,theelectronicabsorptionspectrumofchloroformhasbeenrevisitedafewtimes[3–5].TheintermediatesplittingofthehalogenlonepairionizationpotentialinalkylpolyhalidesimpliesthatRydbergtransi-tionsabovethefirstoneortwobandsareextensivelyoverlapped,makingassignmentsmoredifficultascom-paredtothealkylmonohalides.Thiswasfirstpointedout

ContentslistsavailableatScienceDirectjournalhomepage:www.elsevier.com/locate/jqsrtJournalofQuantitativeSpectroscopy&RadiativeTransfer

0022-4073/$-seefrontmatter&2013ElsevierLtd.Allrightsreserved.http://dx.doi.org/10.1016/j.jqsrt.2013.06.016

nCorrespondingauthor.Tel.:+912225590343;fax:+912225502652.

E-mailaddresses:ashastri@barc.gov.in,aparnaragini@gmail.com(A.Shastri).

JournalofQuantitativeSpectroscopy&RadiativeTransfer129(2013)204–213byRobin[3]whodiscussedtheoverallfeaturesoftheelectronicabsorptionspectraofseveralchloromethanesandcarriedoutqualitativeassignmentsbasedonacom-parativestudy.ThefirstsynchrotronradiationbasedVUVphotoabsorptionstudyofCHCl3wasreportedbyLeeand

Suto[5]inthewavelengthregion105–220nm(45,500–95,000cm−1).AfewoftheobservedbandswereclassifiedintoRydbergseriesandvibronicassignmentsproposedforsomeofthetransitions.However,theassignmentsmadebythemshowseveraldiscrepancies,bothintermsofRydbergseriesaswellasvibronicassignmentsproposed.Forinstance,someoftheintensevibronicfeaturesinthe72,500–76,500cm−1regionareleftunassignedwhereasassignmentshavebeenproposedforrelativelyweakandunresolvedfeatures.Assignmentofthesebandsasbelong-ingtothe3e-4ptransitionalsoisdoubtfulasitimpliesaquantumdefectof󰀁2.1whichisratherhighforachlorineporbital.AmentionalsomustbemadeheretothefluorescencestudiescarriedoutbySeccombeetal.[6].TheyhavemappedthedissociationchannelsofchloroformafterVUVexcitationintheregion8–12eVbymonitoringthedispersedfluorescencefromthedissociationproducts,concludingthatthefluorescenceismainlyfromneutralfragmentsproducedbythedissociationofRydbergstatesoftheparentmolecule.Thermochemicalpathwaysanddissociationdynamicsofneutralandionizedchloroformhavealsobeenstudiedbyavarietyofothertechniqueslikethresholdphotoelectronphotoioncoincidence(TPEPICO)[8],imagingphotoelectronphotoioncoincidencespectro-scopy(IPEPICO)[9]andVUVnegativephotoionspectro-scopy[10].Otherexperimentalstudiesofchloroformofrelevancetoitselectronicabsorptionspectrumincludestudiesofreactionmechanismsusingfemtosecondlaserpulses[11]andelectronimpactstudiesofafewlowlyingexcitedstates[12].Ionizationpotentialsforchloroformandseveralotherhalomethanescorrespondingtoexcita-tionfromthenonbondingporbitalsofthehalogenatomshavebeenreportedbyDixonetal.[13].Onthetheoreticalfront,althoughafewabinitiocalculationshavebeenreportedforchloromethanes[14–16],mostoftheworkislimitedtogroundstateandionizationenergycalculationsandunderstandingoftheelectronicallyexcitedstatesintheVUVregionisgenerallyinadequate.Thepresentworkismotivatedbyaneedtobuildabetterunderstandingofthehigh-lyingexcitedstatesofchloroformparticularlyintheenergyregion6.2–11.8eV.VUVphotoabsorptionstudiesofCHCl3andCDCl3areperformedusingsynchrotronradiationandacompleteRydbergseriesandvibronicanalysisoftheobservedspectrumiscarriedout.TheVUVphotoabsorptionspec-trumofthedeuteratedcompoundCDCl3isreportedhereforthefirsttimeanditservestoconfirmandconsolidateproposedvibronicassignments.Spectralanalysisisaidedbyquantumchemicalcalculations.2.ExperimentalSynchrotronradiationfromthe450MeVstorageringIndus-1atRRCAT,Indoreisdispersedbya1mSeya-Namiokavacuummonochromator,enablinggasphaseabsorptionstudiesintheenergyregion6.2–11.8eV(1050–2000Å)ataresolutionof󰀁6meVat6eVand󰀁10meVat10eV.Theexperimentsarecarriedoutina250mmlongsingle-passstainlesssteelgascellwithsuitableportsforevacuation,pressuremeasurement,sampleintroduction,etc.Thecellisevacuatedtoabasepressureof󰀁10−6mbar.SamplesofCHCl3andCDCl3