You are on page 1of 4

JenniferK.Howell&JenniferPitt-Lainsburyforwww.APchemresources2014.weebly.

com,2013page1of4 page
PhotoelectronSpectroscopyinAPChemistry

Photoelectronspectroscopy,commonlyabbreviatedasPES,isnewlyaddedtotheAPChemistry
curriculumfor2013-14.

BackgroundInformation
1

PESisatechniquetodeterminethebindingenergyofelectronsinanatomormolecule,including
thoseelectronslocatedincoreshells.

e
-
e
-
e
-
e
-
e
-
e
-
incident light
hv
e
-
e
-
e
-
e
-
e
-
e
-
e
-
e
-
ejected electron
w/ kinetic energy KE
Binding Energy = hv - KE

High-energyincidentlight(X-rayorUV)isusedtoejectasingleelectronfromanatom.
2
Thekinetic
energyoftheejectedelectronismeasured.Thedifferencebetweentheenergyoftheincidentlight
andthekineticenergyoftheejectedelectrongivesthebindingenergyofthatelectron.

Inasamplebeingtested,manyatomsarebeinghitwithincidentlight,andthusmanyelectronsare
ejected.Theseelectronswilloriginatefromalloccupiedorbitalsoftheatom.Thebindingenergyforall
ofthedetectedelectronsarecompliedintoaphotoelectronspectrum,wherethenumberofejected
electronsateachbindingenergyisplotted.Byconvention,bindingenergyisplottedonthehorizontal
axisineVorMJ,withenergyDECREASINGfromlefttoright(seeexampleonpage2).

PrinciplesusedtoInterpretPESSpectra:
- allelectronsinthesamesubshellhavethesamebindingenergy(theyarethesamekind)
- thereisonepeakforeverydifferentkindofelectron
- peakheightcorrespondstotherelativenumberofelectronsineachshellofanatom
- aseffectivenuclearchargeincreases,thebindingenergywillincrease
- bindingenergiesofanelectronwilldifferforanatomvs.thesameatominamolecule

1
informationanddiagramtakenfromChemistry:Structure&Dynamics5
th
Edition,pg.89
2
onlyfirstionizationbindingenergiesaremeasured
JenniferK.Howell&JenniferPitt-Lainsburyforwww.APchemresources2014.weebly.com,2013page2of4 page
Example:Thefollowing3questionsrefertothephotoelectronspectrumofneonasshownbelow:
R
e
l
a
t
i
v
e

N
u
m
b
e
r

o
f

E
l
e
c
t
r
o
n
s
1000 800 600 400 200 0
Photoelectron Spectrum of Neon
Binding Energy (eV)
A B
C
www.APchemresources2014.weebly.com
J. K. Howell

1.PeaksA,B,andCrepresentthebindingenergiesofelectronsinwhichsubshellsofneon?
a. 1s,2s,2p
b. 2p,2s,1s
c. 1s,1s,1s
d. 2s,2p,2p

2.WhichofthefollowingstatementsbestaccountsforpeakAbeingfartotheleftofpeaksBandC:
a. theelectronconfigurationofoxygenis1s
2
2s
2
2p
4

b. nitrogenhas8electronslocatedinitsvalenceshell
c. coreelectronsofanatomexperienceamuchhighereffectivenuclearchargethanvalence
electrons
d. peaksBandCshowfirstionizationenergiesofelectronsinneon,whereaspeakAshowsthe
secondionizationenergyofneonelectrons

3.WhichofthefollowingstatementsbestaccountsforpeakCbeingthreetimestheheightofpeakB:
a. theintensityofthephotoelectronsignalatagivenenergyisameasureofthenumberof
electronsinthatenergylevel
b. electronsrepresentedbypeakBhaveapproximatelytriplethebindingenergythanthose
representedbypeakC
c. inaphotoelectronspectrum,asbindingenergyincreasestherelativenumberofelectrons
decreases
d. theheightofpeaksinaphotoelectronspectrumdoesnothaveanyrelationtothestructure
ofanatom

InterpretationofSpectrum:
Thephotoelectronspectrumofneonshowsthattheelectronsinthe1ssubshell(peakA)haveamuch
higherbindingenergy(870eV)thantheelectronsisthe2ssubshell(peakB:49eV)and2psubshell
(peakC:22eV).Additionally,the2psignal(peakC)istheetimestheheightofthe1sand2ssignals
(peakB),indicatingthatitcontainstriplethenumberofelectrons(2p
6
vs.1s
2
/2s
2
).

Answers:1(a),2(c),3(a)
JenniferK.Howell&JenniferPitt-Lainsburyforwww.apchemistryrevisions.weebly.com,2013page3of4

PESandtheQuantumMechanicalModeloftheAtom:
PESdatademonstratesthatenergiesofelectronsinthesameprinciplequantumnumberarenot
degenerate.Thissupportstheexistenceofsub-shellsinthequantummechanicalmodeloftheatom.
TheinterpretationofPESdataalsoincludes:
- numberofsubshellsperprinciplequantumnumberandrelativeenergies
- numberofelectronsthatcanbeheldineachsubshell
- exceptionstotheexpectedelectronfillingofsubshells(copper/chromium)
- whichshellselectronsarebeingremovedfromwiththeformationofions(4svs.4d)

HowisPESincorporatedintotheAPChemistrycurriculum?
ThereisafocusisonreadingPESspectraandbeingabletodrawconclusionsbasedonthe
experimentalobservations.Additionally,thestudentshouldbeabletointerpretandrelatevarious
representationsofthesamedata:electronicconfigurations,PESspectraandbindingenergies
!""#$%&'()*$+,(#-.#)/010/: 1he aLom ls composed of negaLlvely charged elecLrons, whlch can leave Lhe aLom, and a
poslLlvely charged nucleus LhaL ls made up of proLons and neuLrons. 1he aLLracLlon of Lhe elecLrons Lo Lhe nucleus ls Lhe
basls of Lhe sLrucLure of Lhe aLom. Coulomb's law ls quallLaLlvely useful for undersLandlng Lhe sLrucLure of Lhe aLom.
-0 hoLoelecLron specLroscopy (LS) provldes a useful means Lo engage sLudenLs ln Lhe use of quanLum mechanlcs Lo
lnLerpreL specLroscoplc daLa and exLracL lnformaLlon on aLomlc sLrucLure from such daLa. ln parLlcular, low-resoluLlon
LS of aLoms provldes dlrecL evldence for Lhe shell model. LlghL conslsLs of phoLons, each of whlch has energy L = h!,
where h ls lanck's consLanL and ! ls Lhe frequency of Lhe llghL. ln Lhe phoLoelecLrlc effecL, lncldenL llghL e[ecLs
elecLrons from a maLerlal. 1hls requlres Lhe phoLon Lo have sufflclenL energy Lo e[ecL Lhe elecLron. hoLoelecLron
specLroscopy deLermlnes Lhe energy needed Lo e[ecL elecLrons from Lhe maLerlal. MeasuremenL of Lhese energles
provldes a meLhod Lo deduce Lhe shell sLrucLure of an aLom. 1he lnLenslLy of Lhe phoLoelecLron slgnal aL a glven
energy ls a measure of Lhe number of elecLrons ln LhaL energy level.
#0 1he elecLronlc sLrucLure of aLoms wlLh mulLlple elecLrons can be lnferred from evldence provlded by LS. lor
lnsLance, boLh elecLrons ln Pe are ldenLlcal, and Lhey are boLh roughly Lhe same dlsLance from Lhe nucleus as ln P,
whlle Lhere are Lwo shells of elecLrons ln Ll, and Lhe ouLermosL elecLron ls furLher from Lhe nucleus Lhan ln P.
2#'3$&$.)456#7%&8#)/09 1he sLudenL ls able Lo descrlbe Lhe elecLronlc sLrucLure of Lhe aLom, uslng LS daLa, lonlzaLlon
energy daLa, and/or Coulomb's law Lo consLrucL explanaLlons of how Lhe energles of elecLrons wlLhln shells ln aLoms vary.
:7&#$7#);3'7%&7#)/: 1he sLudenL can use represenLaLlons and models Lo communlcaLe sclenLlflc phenomena and solve
sclenLlflc problems.
:;)/0< 1he sLudenL can "#$%&#'"#("#)#&*+*%,&)'+&-'.,-#/)'of naLural or man-made phenomena and sysLems ln Lhe
domaln: descrlblng modlflcaLlons Lo Lhe 8ohr model LhaL are requlred by LS daLa.
:;)/0= 1he sLudenL can "#0#1("#))'2#3'#/#.#&*)'of naLural phenomena across mulLlple represenLaLlons ln Lhe domaln:
readlng phoLoelecLron specLroscopy daLa and Lhen wrlLlng an elecLron conflguraLlon conslsLenL wlLh Lhe daLa, or uslng
Lhe perlodlc Lable Lo predlcL elLher Lhe phoLoelecLron specLrum or Lhe elecLron conflguraLlon.
:7&#$7#);3'7%&7#)<: 1he sLudenL can engage ln sclenLlflc quesLlonlng Lo exLend Lhlnklng or Lo gulde lnvesLlgaLlons wlLhln
Lhe conLexL of Lhe A course.
:;)<0< 1he sLudenL can #!+/4+*#')(#5%$%5'64#)*%,&): are LS daLa conslsLenL wlLh Lhe 8ohr model, or can Coulomb's law
and Lhe shell model be used Lo explaln why Lhe lonlzaLlon energy of na ls hlgher Lhan LhaL of 8b?

JenniferK.Howell&JenniferPitt-Lainsburyforwww.apchemistryrevisions.weebly.com,2013page4of4

ThePhotoelectricEffect:
ThePhotoelectricEffectisthefoundationforPhotoelectronSpectroscopy.Astheincidentlight
increasesinfrequency,moreelectronsareejectedformthesurfaceofthemetal.Thekineticenergyof
theemittedelectrononlyincreaseswithincreasedenergyoftheincidentlight.Thisexperimental
evidencesupportsthetheorythatelectronsinatomsarelocatedinorbitalswithdiscreteenergylevels.

Imagefrom:http://hyperphysics.phy-astr.gsu.edu/hbase/mod1.html
Incidentlight(hv)greaterthan1000eVisconsideredX-rayradiation,andthetechniqueissometimes
calledX-RayPhotoelectronSpectroscopy(XPS).
Incidentlight(hv)between10-100eVisconsideredtobeinthevacuumultravioletspectrum,andthe
techniquemaybecalledUltravioletPhotoelectronSpectroscopy(UPS).

Resources:
Spencer,JamesN.,GeorgeM.Bodner,andLymanH.Rickard.Chemistry:StructureandDynamics.5th
Edition.NewYork:JohnWiley&Sons.2011.Pg.88-94
AnAPChemistrytextbookapprovedbytheCollegeBoard,whichcontainsacomprehensive
sectiononPhotoelectronSpectroscopy.

Ellis,Andrew,MiklosFeher,andTimothyWright.ElectronicandPhotoelectronSpectroscopy:
FundamentalsandCaseStudies.Cambridge;2005.Section1.1andChapter12
Anindepthbackgroundontheoryandvariationsforphotoelectronspectroscopy.Diagramsof
thespectrometeranddetailsontheelectrondetectionmethodsareprovided.Thisresourceis
idealforateachertogainbackgroundinformationonPES,buttooindepthforstudentuse.

http://xdb.lbl.gov/Section1/Table_1-1.pdf
X-RayDataBooklet,bytheCenterforX-rayOpticsAdvancedLightSource;2001.
Atableofelectronbindingenergies,inelectronvolts,forelements1-92intheirnaturalform.
UsefulfordesigningtestquestionsusingauthenticXPSdata.Doesnotcontainbindingenergies
forvalenceelectrons.

http://www.colby.edu/chemistry/PChem/Lecture2.html-GotoAtomicOrbitalIonizationEnergylink
AtomicOrbitalIonizationEnergiesTableineV,takenfromElectronsandChemicalBonding,
Benjamin,1964,Appendix