Laser Experiments for Chemistry and Physics

415 Pages·2016·140.47 MB·English

by  Robert N. Compton, Michael A. Duncan

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