Laser Experiments for Chemistry and Physics PDF
Preview Laser Experiments for Chemistry and Physics
LASER EXPERIMENTS FOR CHEMISTRY AND PHYSICS Laser Experiments for Chemistry and Physics Robert N. Compton and Michael A. Duncan 3 3 GreatClarendonStreet,Oxford,OX26DP, UnitedKingdom OxfordUniversityPressisadepartmentoftheUniversityofOxford. ItfurtherstheUniversity'sobjectiveofexcellenceinresearch,scholarship, andeducationbypublishingworldwide.Oxfordisaregisteredtrademarkof OxfordUniversityPressintheUKandincertainothercountries ©RobertN.ComptonandMichaelA.Duncan2016 Themoralrightsoftheauthorshavebeenasserted FirstEditionpublishedin2016 Impression:1 Allrightsreserved.Nopartofthispublicationmaybereproduced,storedin aretrievalsystem,ortransmitted,inanyformorbyanymeans,withoutthe priorpermissioninwritingofOxfordUniversityPress,orasexpresslypermitted bylaw,bylicenceorundertermsagreedwiththeappropriatereprographics rightsorganization.Enquiriesconcerningreproductionoutsidethescopeofthe aboveshouldbesenttotheRightsDepartment,OxfordUniversityPress,atthe addressabove Youmustnotcirculatethisworkinanyotherform andyoumustimposethissameconditiononanyacquirer PublishedintheUnitedStatesofAmericabyOxfordUniversityPress 198MadisonAvenue,NewYork,NY10016,UnitedStatesofAmerica BritishLibraryCataloguinginPublicationData Dataavailable LibraryofCongressControlNumber:2015939606 ISBN978–0–19–874297–5(hbk.) ISBN978–0–19–874298–2(pbk.) Printedandboundby CPIGroup(UK)Ltd,Croydon,CR04YY LinkstothirdpartywebsitesareprovidedbyOxfordingoodfaithand forinformationonly.Oxforddisclaimsanyresponsibilityforthematerials containedinanythirdpartywebsitereferencedinthiswork. Preface Likemostscientists,theauthorsofthistextbookhavebeengreatlyinfluencedby theiracademicbackgroundsandmentors.DuncanandComptonwerebothun- dergraduatestudentsinsmallliberalartscolleges(FurmanUniversityandBerea College, respectively) in which student research was a vital part of their educa- tional experience. Performing undergraduate research was of equal importance to course work. Both authors began their research careers at the time of the development of the laser and were witness to many incredible advances in the developmentandapplicationsofthisnewtechnology. Ingraduateschool,Comptonwasparticularlyinfluencedbythefirstyearex- perimentalresearchcourserequiredofeveryincominggraduatestudent(theory orexperiment)intheDepartmentofPhysicsattheUniversityofFlorida.Inad- ditiontoexperiments,ProfessorAlexGreenincludedglassblowingandmachine shopfundamentalsinthiscourse.Althoughitisnotarequiredcourse,asimilar experienceisofferedtothephysicsandchemistrygraduatestudentsattheUni- versityofTennessee(UT)byCompton.Someoftheseexperimentsareincluded inthisbook.Inafewinstances,thelaboratoryexperimentsresultedinanareaof research.Forexample,intheundergraduatelaboratoriesstudentswererequired torecordandanalyzeaRamanspectrumofCCl atroomtemperature.Dueto 4 thethermalrovibrationalpopulation,theStokeslinesareverybroadatroomtem- perature.ToresolvetheisotopelinesofCCl ,oneofthestudentsintheadvanced 4 physicslaboratory(DarrinEllis)recordedaRamanspectrumofCCl submerged 4 underliquidnitrogeninaStyrofoamcup.Duetorovibrationalcooling,thespec- trum of CCl under liquid nitrogen shows fully resolved isotopic contributions 4 due to the 35Cl and 37Cl isotopes (see Chapter 18, Figure 18.3). A number of papershaveappearedillustratingtheadvantagesandutilityofRamanUnderNi- trogen(RUN).Asagraduatestudentin1962workingunderG.S.Hurstatthe Oak Ridge National Laboratory, Compton was privileged to purchase and use oneofthefirstcommercial(BendixCorporation)time-of-flightmassspectrom- eters (TOF-MS). His thesis employed electron impact ionization, but after the developmentofthepulsedlaserComptonintegratedmanyhome-builtTOF-MS instruments into laser ionization experiments at ORNL and UT. In 1979, col- leaguesJ.A.D.StockdaleandComptonformedascientificinstrumentscompany inOakRidgeknownasComstock,whichmanufacturedandsoldTOFsaswellas electrostaticenergyanalyzers(ESAs).Manyoftheseinstrumentshavebeenused byresearchersaroundtheworldtorecordmultiphotonionizationmassandpho- toelectron spectra. This company has employed a number scientists, engineers, andmachinists,whichhasenrichedtheirlivesaswellasscienceingeneral. vi Preface AsanundergraduateatFurman,DuncanlearnedtosolderfromProfessorLon Knightandtogethertheybuiltavacuumsystemformatrixisolationexperiments andEPRstudiesofunusualradicals.AtRiceUniversityinthegroupofRichard Smalley,hewasgiventhetaskofdesigningandbuildingtheirfirsttime-of-flight massspectrometer.Withvirtuallynoelectronicsbackground,Duncanwasguided by the electronics shop to the classic paper by Wiley and McLaren (Rev. Sci. Instrum.26,1150(1955)).Aftermanydesignpitfallsandburned-outcircuits,he eventually madea workinginstrumentandincorporateditintotheir supersonic molecularbeammachine.OtherexperimentsandamisalignedNd:YAGlaserled inadvertentlytothediscoveryofthelaservaporizationmethodusedtoproduce gas-phaseclustersofmetalatomsandotherrefractoryelements.Itwasthislaser vaporization method and the same mass spectrometer that were later employed byJimHeathandSeanO'BrienintheSmalleygrouptodiscoverC .AtGeorgia, 60 Duncan has continued to design and implement new versions of time-of-flight mass spectrometers into his research, and has also developed new experiments fortheundergraduatelabsusingtheseinstruments,manyofwhichareincluded inthisbook. Theauthorshaveemployedmanykindsofmodernlasersandlasertechniques intheirresearchandteachinglaboratories.Comptonwasoneofthefirsttostudy and employ nonlinear optical processes in atomic and molecular research and someofthisearlyworkisfoundinthechaptersdescribingmultiphotonionization, stimulated electronic Raman scattering (SERS), and third harmonic generation (THG).Duncanhasemployedphotoionization,laserdesorptionanalysisofma- terials, and mass-selected ion photodissociation measurements throughout his research.Bothauthorshavedevelopedadvancedphysicalchemistrylaboratories attheirrespectiveuniversitiesandaredeeplyindebtedtothenumerousstudents who have passed through these laboratories, many of whom are now directing theirownphysicalchemistryorphysicslaboratoriesatotheruniversities. Thisbookisdesignedtointroduceresearcherstothebreadthofavailableex- perimentsinchemicalphysicsthatcanbeintegratedintophysicsandchemistry laboratories.Theauthorshavetriedtoincludechaptersthatarefundamentalto lasers and spectroscopy and provide theoretical background to the experiments described.Forexample,thechaptersonpropertiesoflight,diffraction,etc.,and rovibrational spectroscopy should be read before considering the experiments describing IR and Raman spectroscopy, optical activity, and other laser-based experiments. We hope that the enjoyment of laser experiments and their role in advancing chemistry and physics can be appreciated by a new generation of scientiststhroughtheexperimentspresentedhere. RobertN.Compton,Knoxville,TN MichaelA.Duncan,Athens,GA Acknowledgments Theauthorsaregratefultothemanygraduateandundergraduatestudentswho haveworkedintheirlabsovertheyearsandhavecontributedtotheexperiments describedhere.SpecialrecognitionisduetothemanyTeachingAssistantswho implemented these experiments in the undergraduate and graduate laboratories attheUniversityofTennesseeandtheUniversityofGeorgia.MADwouldliketo thankProfessorsLionnelCarreiraandAllenKing,whosharedideasandprovided feedbackforlabexperimentsearlyinhiscareeratGeorgia.RNCisindebtedto Professor Charles Feigerle for collaborations on the study of MPI of molecu- lar iodine, to Dr. Donald Armstrong, Dr. Stewart Hager, and Dr. Jeffery Steill (Sandia Laboratory) for assisting with recording the numerous FTIR spectra, and to Dr. James Parks for sharing an experiment from the advanced physics laboratoriesatUT.Specialthanksarealsoduetoformermastersdegreestudent DarrenEllisforperformingthefirstRUNspectruminourlaboratoriesatUT. We would also like to acknowledge the special help in preparing this manu- scriptfromMr.JonathanManer(proofreading),Ms.AlexOrlowsky(figureprep- aration), Mr. Joshua Marks (photography), Mr. Timothy Ward and Mr. David McDonald(computationalwork),andMr.IvanGeigerman(figurepreparation). WearealsogratefultoDrs.SharaniRoyandJayAgarwalforacriticalassessment of Chapter 15 on quantum chemistry calculations. Dr. Paul Siders is gratefully acknowledgedforcontributionstoChapter22onFermiresonances. Table of Contents Part I Introduction to Light, Lasers, and Optics 1 ElementaryPropertiesofLight 3 2 BasicOptics 28 3 GeneralCharacteristicsofLasers 53 4 LaboratoryLasers 63 5 NonlinearOptics 88 6 LaserSafety 102 Part II Laser Experiments for Thermodynamics 7 TheSpeedofLight 115 8 TheSpeedofSoundinGases,Liquids,andSolids 122 9 ThermalLensCalorimetry 144 10 LaserRefractometry 152 Part III Laser Experiments for Chemical Analysis 11 Laser-InducedBreakdownSpectroscopy 159 12 LaserDesorptionTime-of-FlightMassSpectrometry 167 13 MultiphotonIonizationMassSpectrometryofMetalCarbonyls 198 Part IV Laser Experiments for Quantum Chemistry and Spectroscopy 14 OpticalSpectroscopy 207 15 QuantumChemistryCalculations 243 16 MultiphotonIonizationandThirdHarmonicGenerationinAlkaliAtoms 259 17 ElectronicAbsorptionSpectroscopyofMolecularIodine 273 18 ElectronicSpectroscopyofIodineUsingREMPI 280 19 RamanSpectroscopyUnderLiquidNitrogen 288
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