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ElectronaffinityWikipedia,thefreeencyclopedia

Electronaffinity
FromWikipedia,thefreeencyclopedia

Inchemistryandatomicphysics,theelectronaffinityofanatomormoleculeisdefinedastheamountof
energyreleasedorspentwhenanelectronisaddedtoaneutralatomormoleculeinthegaseousstatetoforma
negativeion.[1]
X+eX+energy
Insolidstatephysics,theelectronaffinityforasurfaceisdefinedsomewhatdifferently(seebelow).

Contents
1 Measurementanduseofelectronaffinity
1.1 Signconvention
2 Electronaffinitiesoftheelements
3 Molecularelectronaffinities
4 "Electronaffinity"asdefinedinsolidstatephysics
5 Seealso
6 References
7 Externallinks

Measurementanduseofelectronaffinity
Thispropertyismeasuredforatomsandmoleculesinthegaseousstateonly,sinceinasolidorliquidstates
theirenergylevelswouldbechangedbycontactwithotheratomsormolecules.Alistoftheelectronaffinities
wasusedbyRobertS.Mullikentodevelopanelectronegativityscaleforatoms,equaltotheaverageofthe
electronaffinityandionizationpotential.[2][3]Othertheoreticalconceptsthatuseelectronaffinityinclude
electronicchemicalpotentialandchemicalhardness.Anotherexample,amoleculeoratomthathasamore
positivevalueofelectronaffinitythananotherisoftencalledanelectronacceptorandthelesspositivean
electrondonor.Togethertheymayundergochargetransferreactions.

Signconvention
Touseelectronaffinitiesproperly,itisessentialtokeeptrackofsign.Foranyreactionthatreleasesenergy,the
changeEintotalenergyhasanegativevalueandthereactioniscalledanexothermicprocess.Electron
captureforalmostallnonnoblegasatomsinvolvesthereleaseofenergy[4]andthusareexothermic.The
positivevaluesthatarelistedintablesofEeaareamountsormagnitudes.Itistheword,releasedwithinthe
definitionenergyreleasedthatsuppliesthenegativesigntoE.ConfusionarisesinmistakingEeaforachange
inenergy,E,inwhichcasethepositivevalueslistedintableswouldbeforanendonotexothermicprocess.
TherelationbetweenthetwoisEea=E(attach).
However,ifthevalueassignedtoEeaisnegative,thenegativesignimpliesareversalofdirection,andenergyis
requiredtoattachanelectron.Inthiscase,theelectroncaptureisanendothermicprocessandtherelationship,
Eea=E(attach)isstillvalid.Negativevaluestypicallyariseforthecaptureofasecondelectron,butalsofor
thenitrogenatom.
TheusualexpressionforcalculatingEeawhenanelectronisattachedis

E =(E

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Eea=(EinitialEfinal)attach=E(attach)
ThisexpressiondoesfollowtheconventionX=X(final)X(initial)sinceE=(E(final)E(initial))=
E(initial)E(final).
Equivalently,electronaffinitycanalsobedefinedastheamountofenergyrequiredtodetachanelectronfroma
singlychargednegativeion,[1]i.e.theenergychangefortheprocess
XX+e
Ifthesametableisemployedfortheforwardandreversereactions,withoutswitchingsigns,caremustbetaken
toapplythecorrectdefinitiontothecorrespondingdirection,attachment(release)ordetachment(require).
Sincealmostalldetachments(require+)anamountofenergylistedonthetable,thosedetachmentreactions
areendothermic,orE(detach)>0.

Electronaffinitiesoftheelements
AlthoughEeavariesgreatlyacrosstheperiodictable,somepatterns
emerge.Generally,nonmetalshavemorepositiveEeathanmetals.Atoms
whoseanionsaremorestablethanneutralatomshaveagreaterEea.
Chlorinemoststronglyattractsextraelectronsmercurymostweakly
attractsanextraelectron.Theelectronaffinitiesofthenoblegaseshavenot
beenconclusivelymeasured,sotheymayormaynothaveslightlynegative
values.

EAvsAtomicNumber

Eeagenerallyincreasesacrossaperiod(row)intheperiodictable.Thisiscausedbythefillingofthevalence
shelloftheatomaGroup17atomreleasesmoreenergythanaGroup1atomongaininganelectronbecauseit
obtainsafilledvalenceshellandthereforeismorestable.
AtrendofdecreasingEeagoingdownthegroupsintheperiodictablemightbeexpected.Theadditional
electronwillbeenteringanorbitalfartherawayfromthenucleus.Sincethiselectronisfartherfromthenucleus
itislessattractedtothenucleusandwouldreleaselessenergywhenadded.However,aclearcounterexampleto
thistrendcanbefoundinGroup2,andinspectingtheentireperiodictable,itturnsoutthattheproposedtrend
onlyappliestoGroup1atoms.
Thus,electronaffinityfollowstheleftrighttrendofelectronegativitybutnottheupdowntrend.
ThefollowingdataarequotedinkJ/mol.Elementsmarkedwithanasteriskareexpectedtohavenegativeor
nearzeroelectronaffinitiesonquantummechanicalgrounds.

Electronaffinitiesintheperiodictable
Group
Period

1
2
3
4
5

10

11

12

13

14

15

16

17

18

He

73

1894

Li

Be

60

231

27

Na Mg

Al

Si

53

42

134

72

200

349 1106

Ca

Sc

Ti

Cr

Mn

Fe

Co

Ni

Cu

Zn

Ga

Ge

As

Se

Br

Kr

48

18

51

65

(96)

15

64

112

119

41

119

79

195

324

Rb

Sr

Zr

Nb Mo

Tc

Ru

Rh

Pd

Ag

Cd

In

Sn

Sb

Te

Xe

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122 134 141

Ne

328

Cl

Ar

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47

Cs
46

30

41

86

72

Ba

Hf

Ta

Re

Os

Ir

14

(11)

31

79

14

104

150

Fr

Ra

Rf

Db

Sg

Bh

Hs

Mt

Ds

Rg

(47)

(173)

La

Ce

Pr

Nd

Gd

Tb

Dy

Ho

Er

Tm

Yb

Lu

45

55

93

(16) (12) (16)

99

33

Ac Th

Pa

Np

No

Lr

101

110

Pm Sm Eu
11

54

126

39

107

101

Pt

Au

Hg

Tl

Pb

Bi

205

223

36

35

91

Fl

(13) (42) (34) (33) (30)

Pu Am Cm Bk

Cn Uut

Cf

Es

295

(5)

Po

At

Rn

(127) (269)

Uup Lv

Fm Md

190

Uus Uuo
(5)

Legend
ThenumbermentionedisElectronaffinityinkJ/mol(rounded)
FortheequivalentvalueineV,see:Electronaffinity(datapage)
*Denoteselementsthatareexpectedtohavenegativeornearzeroelectronaffinitiesonquantummechanical
grounds
Parenthesesdenotepredictions
Primordial

Fromdecay

Synthetic

Bordershowsnaturaloccurrenceoftheelement

Backgroundcolorshowssubcategoryinthemetalmetalloidnonmetaltrend:
Metal
Nonmetal
Unknown
Alkaline
Post
Metalloid Polyatomic Diatomic
chemical
Alkali
Lan
Transition
earth
Actinide
transition
Noblegas
properties
metal
thanide
metal
nonmetal nonmetal
metal
metal

Molecularelectronaffinities
Theelectronaffinityofmoleculesisacomplicatedfunctionoftheirelectronicstructure.Forinstancethe
electronaffinityforbenzeneisnegative,asisthatofnaphthalene,whilethoseofanthracene,phenanthreneand
pyrenearepositive.Insilicoexperimentsshowthattheelectronaffinityofhexacyanobenzenesurpassesthatof
fullerene.[5]

"Electronaffinity"asdefinedinsolidstatephysics
Inthefieldofsolidstatephysics,theelectronaffinityisdefineddifferentlythaninchemistryandatomic
physics.Forasemiconductorvacuuminterface(thatis,thesurfaceofasemiconductor),electronaffinity,
typicallydenotedbyEEAor,isdefinedastheenergyobtainedbymovinganelectronfromthevacuumjust
outsidethesemiconductortothebottomoftheconductionbandjustinsidethesemiconductor:[6]

Inanintrinsicsemiconductoratabsolutezero,thisconceptisfunctionallyanalogoustothechemistrydefinition
ofelectronaffinity,sinceanaddedelectronwillspontaneouslygotothebottomoftheconductionband.At
nonzerotemperature,andforothermaterials(metals,semimetals,heavilydopedsemiconductors),theanalogy
doesnotholdsinceanaddedelectronwillinsteadgototheFermilevelonaverage.Inanycase,thevalueofthe
electronaffinityofasolidsubstanceisverydifferentfromthechemistryandatomicphysicselectronaffinity
valueforanatomofthesamesubstanceingasphase.Forexample,asiliconcrystalsurfacehaselectronaffinity
4.05eV,whereasanisolatedsiliconatomhaselectronaffinity1.39eV.
Theelectronaffinityofasurfaceiscloselyrelatedto,butdistinctfrom,itsworkfunction.Theworkfunctionis
thethermodynamicworkthatcanbeobtainedbyreversibly,isothermallymovinganelectronfromthevacuum
tothematerialthisthermodynamicelectrongoestotheFermilevelonaverage,nottheconductionbandedge:
.Whiletheworkfunctionofasemiconductorcanbechangedbydoping,theelectronaffinity
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ideallydoesnotchangewithdopingandsoitisclosertobeinga
materialconstant.However,likeworkfunctiontheelectronaffinitydoes
dependonthesurfacetermination(crystalface,surfacechemistry,etc.)
andisstrictlyasurfaceproperty.
Insemiconductorphysics,theprimaryuseoftheelectronaffinityisnot
actuallyintheanalysisofsemiconductorvacuumsurfaces,butratherin
heuristicelectronaffinityrulesforestimatingthebandbendingthat
occursattheinterfaceoftwomaterials,inparticularmetal
semiconductorjunctionsandsemiconductorheterojunctions.
Incertaincircumstances,theelectronaffinitymaybecomenegative.[7]
Oftennegativeelectronaffinityisdesiredtoobtainefficientcathodes
thatcansupplyelectronstothevacuumwithlittleenergyloss.The
observedelectronyieldasafunctionofvariousparameterssuchasbias
voltageorilluminationconditionscanbeusedtodescribethese
structureswithbanddiagramsinwhichtheelectronaffinityisone
parameter.Foroneillustrationoftheapparenteffectofsurface
terminationonelectronemission,seeFigure3inMarchywkaEffect.

Banddiagramofsemiconductor
vacuuminterfaceshowingelectron
affinityEEA,definedasthe
differencebetweennearsurface
vacuumenergyEvac,andnearsurface
conductionbandedgeEC .Also
shown:FermilevelEF,valenceband
edgeEV,workfunctionW.

Seealso
Ionizationenergyacloselyrelatedconceptdescribingtheenergyrequiredtoremoveanelectronfrom
aneutralatomormolecule
Oneelectronreduction
Electroncapturemassspectrometry
Electronegativity
Valenceelectron
Vacuumlevel
Electrondonor

References
1.IUPAC,CompendiumofChemicalTerminology,2nded.(the"GoldBook")(1997).Onlinecorrectedversion:
(2006)"Electronaffinity(http://goldbook.iupac.org/E01977.html)".
2.RobertS.Mulliken,JournalofChemicalPhysics,1934,2,782.
3.ModernPhysicalOrganicChemistry,EricV.AnslynandDennisA.Dougherty,UniversityScienceBooks,2006,
ISBN9781891389313
4.ChemicalPrinciplestheQuestforInsight,PeterAtkinsandLorettaJones,Freeman,NewYork,2010ISBN9781
429219556
5.Remarkableelectronacceptingpropertiesofthesimplestbenzenoidcyanocarbons:hexacyanobenzene,
octacyanonaphthaleneanddecacyanoanthraceneXiuhuiZhang,QianshuLi,JustinB.Ingels,AndrewC.Simmonett,
StevenE.Wheeler,YaomingXie,R.BruceKing,HenryF.SchaeferIIIandF.AlbertCottonChemical
Communications,2006,758760Abstract(http://dx.doi.org/10.1039/b515843e)
6.Tung,RaymondT."FreeSurfacesofSemiconductors".BrooklynCollege.
7.Himpsel,F.Knapp,J.Vanvechten,J.Eastman,D.(1979)."Quantumphotoyieldofdiamond(111)Astable
negativeaffinityemitter".PhysicalReviewB.20(2):624.Bibcode:1979PhRvB..20..624H.
doi:10.1103/PhysRevB.20.624.

Tro,NivaldoJ.(2008).Chemistry:AMolecularApproach(2ndEdn.).NewJersey:PearsonPrentice
Hall.ISBN0131000659.pp.348349.

Externallinks
Electronaffinity(http://goldbook.iupac.org/E01977.html),definitionfromtheIUPACGoldBook
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