The Basics of Quantum Mechanics: 1.1 Why Quantum Mechanics Is Necessary For Describing Molecular Properties

C h a p t e r1
The basicsof quantum mechanics
1.1 Why quantum mechanicsis necessaryfor describing

molecularproperties
we krow that all molcculesare made of atoms which. in turn. containnu-
clei and electrons.As I discussin this introcjuctory
section,the equationsthat
govern the motions of electronsand of nuclei are not the familiar Newton
equatrons.
F:ma (l.l)
but a nervset of equationscalledSchrodingerequations.when scientistsfirst

studiedthe behaviorof electronsand nuclei.thev tried to interprettherr ex-
perimentalfindin-ssin termsof classicalNewtonianmotions.but suchatrempts
eventuallyfailed.Theyfoundthatsuchsrnalllightparticlesbehaved in a waythat
simply is not consistent rvith the Neu'tonequations. Let me norvillustratesorne
ofthe experimentaldatathat gaverise to theseparadoxesand shorvyou how the
scientists ofthoseearlytimesthenusedthesedataro suggestnew equatrons that
theseparticlesrnight obcy.I want to stressthat the Schrcidinger equationwas not
derivedbut postulated by thesescientists. In fact,to date,rlo one hasbeenable
t o d e r i r et h e S c h r c i d i n geeqr u a t i o n .
Fron.rthe pioneeringwork of Braggon ditrractionof x-raysfiom planesof
atomsor ions in crvstals,it was knownthat peaksin the intensityof ditliacted
x-rayshavin,u wavelength i rvouldoccurat scattering anglesg determinedby the
larnousBragg equation:
nt : 24 tinp (1.2)
where d is the spacingbetweenneighborin,u planesof atomsor ions. These

quantitiesare illustratedin Fig. I . I . Therearemany suchdiffractionpeaks,each
l a b e l e d b y a d i f f e r e n t v a l utehoefi n r e g en r( n - 1 , 2 . 3 , . . . ) . T h e B r a - s - q f o r m u l a
can be derivedby consideringwhen two photons,one scatteringfrom the second
plane in the figure and the secondscatteringfrom the third plane,will undergo
constructiveinterference.This condition is met when the ,.extrapath leneth,'
T h e b a s i c so f o u a n t u mm e c h a n i c s
Scatteringof
t w o b e a m sa t a n g l e6
f r o m t w o p l a n e si n a
crystalspacedby d.
coveredby the secondphoton (i.e.,the lengthfront pointsA to B to C; is an

integermultipleof the wavelengthof the photons.
The importance of thesex-rayscatterin_e experiments to the studyof electrons
and nuclei appearsin tl.reexperirnentsof Davissonand Gernter.in 1927, u'ho
scatteredelectronsof(reasonably) fixedkineticenerg)'E from metalliccrvstals.
Theseworkersfoundthatplotsofthenumberofscattered electrons asa functionof
scattering
angled displayed "peaks"
atangles6 thatobeyeda Bragg-likeequation.
The startlingthing aboutthis observation is that electronsare particles.vet the
Bragg equationis basedon the propertiesof waves.An important observation
derivedfron.rthe Davisson-Germerexperimentswas that the scatteringangles6
observedfor electronsof kinetic energ.vE couldbe fit to the Braggni, : 2d sin0
equationif a wavelengthwere ascribedto theseelectronsthat u'asdefinedby
)":hl(2m"E)t'2. (1.3)
where rl. is the massof the eiectronand i is the constantintroducedby Max

Planckand Albert Einsteinin the eariy 1900sto relatea photon'senergv,Eto
its frequencyy I'ia .E : /rt,. Theseamazingfindingswere amongthe earliestto
suggestthat electrons,u,hich had alwaysbeen viewed as particles,might have
somepropertiesusually ascribedto waves.That is. as de Broglie suggestedin
1925,an electronseemsto havea wavelengthinverselyrelatedto its momenfum,
andto displaywave-typediffraction.I shouldmentionthat analogousdiffraction
u'asalsoobservedwhenothersmalllight particles(e.g.,protons.neutrons,nuclei,
and small atomic ions) were scatteredfrom crystal planes.In all such cases,
Bragg-likediffractionis observedand the Bragg equationis found to governthe
scatteringanglesifone assignsa wavelengthto the scatteringparticleaccordingto
),:hlQmE)1t2, (1.4)
where rl is the mass of the scatteredparticle and /r is Planck's consranr

( 6 . 6 2x l 0 - 2 7e r gs ) .
W h y q u a n t u mm e c h a n i c si s n e c e s s a rfyo r d e s c r i b i n gm o l e c u l a rp r o p e r t i e s
l,.inm
- c
a h
c a
ot c
c
I VisibleI
*.'{fllllrilt-Irffi
frlllill ""'-*,,-onllrll spectrumof atomic
Emission
Anarvsis Paschen h y d r o g e nw i t h s o m e
lrrn lines repeatedbelow to
illustrate t h e s e r i e st o
Llf Brackett w h i c ht h e y b e l o n g .
Theobservation thatelectronsandothersmalllight particlesdisplayivave-like

behavior r.vas
important because theseparticlesarewhatall atomsandmolecules
are made of. So, if we want to fully understandthe motions and behaviorof
molecules.rvemustbe surethat*e can adequately describesuchpropertiesfor
theirconstitr"rents.
Because the classical
Newtonecluations do not containtactors
that sr-rggcst
wave propertiesfor electronsor nuclei mo'",ingfreely in space.the
abovebehaviorspresented significantchallenges.
Anotherproblemthat arosein earlystudiesof atomsand moleculesresulted
fiom the stLrdyof the photonsemittedfrom atomsand ions that had beenheated
or otherr.iseexcited(e.g.,by electricdischarge).It was found that eachkind
of atom (i.e.,H or C or O) ernittedphotonsrvhosefrequencies u wereof very
characteristicvalues.An exampleof suchemissionspectrais shownin Fig. I .2
fbr hydrogenatoms.In the top panel,we seeall of the linesemittedwith thcir
wavelengths indicatedin nanometers. The other panelsshow horvtheselines
havebeenanalyzed(by scientists rvhosenarnesareassociated) into patternsthat
relateto the specilicenergylevelsbetweenwhich transitionsoccurto emit the
corresponding photons.
In theearlyattemptsto rationalizesuchspectrain termsof electronicmotlous.
one describedan electronas rnovinsaboutthe atomicnuclei in circularorbits
such as shor.vn in Fig. 1.3.A circularorbit was thoughtto be stablewhen the
outwardcentrifugalfbrcecharacterized by radiusr. and speedu (rr.u2/r) on the
electronperf-ectlir
counterbalanced theinwardattractit,eCoulombforce(Ze2 l121
exertedby the nucleusof chargeZ:
-
n.r- ,'t' = Ze-lt . (1 . 5 )
This equation,in turn, allows one to relatethe kinetic energy lrr.ul to the
CoulornbicenergyZe2lr, and thusto expressthe t o t a le n e r g yE o f a n o r b i t i n
T h e b a s i c so f q u a n t u mm e c h a n i c s
terrnsof the radiusof the orbit:

I -l
E : - r t t . . r -- Z t ' - , r ' : - Z L ' -/ t ' . (1.6)
f ' ' 1
The energycharacterizingan orbit ofradius r. relatil'eto the 6 : 0 reference

of energyat r --+ 3p. becomesmore andmore negative(i.e.,lorverandlou,er)asr
becomessmaller.This relationshipbetweenoutu'ardand inu,ardforcesallou's
one to concludethat the electronshouldrnovefasteras it movescloserto the
nucleussincer'2 : Ze7l(rntr). Howeter.noq'herein this mclclel is a conceptthat
relatesto the experimental fact that eachatoll erltitsonll'certainkindsof pho-
C h a r a c t e r i z a t i o no f tons.lt u'asbelievedthatphotoner.nission occurreduficn an electronr.rrovirrr irr
small and large stable a largercircularorbit lostenergyandnrovedto a sn.raller circularorbit.Hor.r'ever.
orbits of radii 11 and 12 the Newtoniandynamicsthatproducedthe aboveequationr.vould allou'orbrtsof
for an electron moving
arouno a nucleus. any radius.and henceany energy.to be follorved.Thus"it wouldappcartlratthe
electronshouldbe ableto emit photonsof any encrgyas it movedfi'omorbit to
orbit.
The breakthroughthat allowed scientistssuch as Niels Bohr to apply the
circular-orbitmodel to the observedspectraldata invol','edfirst introducinsthe
ideathat the electronhas a wavelengthand that this u'avelensthi is relatedto
its nromentumby the de Broglie equationL- hlp. The key stepin the Bohr
model u'asto also specifythat the radiusof the circularorbit be suchthat the
cilcurnference of the ctrcle2nr equalan integer(n) multipleof theu'avelen-gth i.
Only in this way will the electron'svu'ave
experienceconstructiveinterferenceas
the electronorbits the nucleus.Thus, the Bohr relationshipthat is analogousto
the Bragg equationthat determinesat what anglesconstructiveinterferencecan
occuris
2 t r r: n ) . . (1.7)
Both this equationandthe analogousBraggequationare illustrationsof what we

call boundaryconditions;they are extra conditionsplacedon the wavelengthto
producesomedesiredcharacterin the resultantwave( in thesecases,constructile
interference).Of course,there remains the questionof why one must impose
theseextra conditionswhen the Neu,toniandynamicsdo not requirethem. The
resolutionof this paradoxis one of the thingsthat quantummechanicsdoes.
R e t u r n i n g t ot h ea b o v ea n a l y s i as n du s i n gl , : h l p : h l ( m v ) . 2 r r : 4 ) ' , s g
weli as the force-balanceequationm"r2 1, : Z e2I 12, one can then solvefor the
radii that stableBohr orbits obey:
y :1nhl2n)2 /(m"Ze2) (l 8)
and, in turn. for the velocities ofelectrons in these orbits,
v : ze2lfuhl2tr). (l . e )
W h y q u a n t u mm e c h a n i c si s n e c e s s a r fyo r d e s c r i b i n gm o l e c u l a rp r o p e r t i e s
Thesetrvo resultsthen allorv one to expressthe sum ofthe k i n e t i c( l r r . r ' : ) a n c l

Coulombpotential(-Ze2 lrl energies as
g : - ! r , , z t r ' 1 t n l1t 2 t1 ' . (1.r0)

) '
Just as in the Bragg diflraction result,rvhich specifiedat what anglesspecial

high intensitiesoccurredin the scattering, there are many stableBohr orbits.
each labeledby a value of the integer ir. Those with small n have small
radii. high velocitiesand more negativetotal energies(n.b., the reference
zero of energycorrespondsto the electronat r : oc, and with v :0). So.
"allowed" that causes
it is the resultthat only certainorbits are only certain
energiesto occur and thus only certain energiesto be observedin the emitted
photolls.
It turnedout that the Bohr formula for the energylevels(labeledby r) of
an electronmoving abouta nucleuscould be usedto explainthe discreteline
e m i s s i osnp e c t roaf r l l o n e - e l e c t r o
ant o m sa n d i o n s{ i . e . .H . H e . L i - : . e t c . ) t o
veryhighprecision.in suchan interpretation of theexperimental data.oneclaims
that a photonof energy
hv=R(tlni-rlni) (l.lr)
is emittedrvhenthe atom or ion undergoesa transitionfiom an orbit having

quantumnumberni to a lower-energy orbit havingnf. Herethe symbolR is used
to denotethe fbllo*ing collectionof factors:
I
R - -nt,Z-e*llltr)tl' (1.12)
The Bohr formulafbr energylevelsdid not agreeaswell w ith the observedpattern

of emissionspectrafor speciescontainingmorethana singleelectron.However,
it doesgive a reasonable fit, for example.to the Na atomspectraif oneexamrnes
only transitionsinvolvingthe singlevalenceelectron.The primary reasonfor
the breakdorvn of the Bohr formulais the neglectof electron-electron Coulomb
repulsionsin its derivation. Nevertheless.the success of this modelmadeit clear
thatdiscreteemissionspectracouldonly be explainedby introducingtheconcept
thatnot all orbitswere"allowed".Only specialorbitsthatobeyeda constructive-
intert-erence conditionwerereallyaccessible to the electron'smotions.This idea
that not all energiesrverealloweclbut only certain "quantized" energiescould
occur was essentialto achievingevena qualitativesenseof agreementr.viththe
experimentalfact that emissionspectrawerediscrete.
In summary,two experimentalobservationson the behaviorof electronsthat
were crucial to the abandonmentof Newtoniandynamicswere the observations
of electrondiffractionand of discreteemissionspectra.Both of thesefindings
seem to suggestthat electronshave some wave characteristicsand that these
waveshaveonly certainallowed(i.e.,quantized)wavelengths.
So. nou, rve havesome idea why the Newton equationsfail to accountfor
the dynan.ricalnrotionsof light and small;lartrclessuchas electronsand nuclei.
We seethat extraconditions(e.g..the Braggconditionor constraints on the de
Brogiieu'avelength) couldbe imposedto achievcsome degree of agreenrenlu'ith
experimental observation. u'estill arelcft wonderingr.ihattheequations
Hou'e'u'er,
are that can be appliedto properlydescribesuch motior.rs and why the extra
conditions areneeded. It turnsoutthata ner.r'kind of equationbasedon cornbining
u'aveandparticleproperties neededto be developed to address suchissues. These
arethe so-calledSchrddinger equationsto ri'hichwe no\\'tunr our attention.
As I saidearlier.no one hasvet shownthat the Schrodi-qer equationfollou,s
deductivelirfrom somen.rorefundamentaltheory.That is. scientistsdid not de-
theypostulatedit. Sorre ideaof hou'the scientists
rive this equatiotr; o1'thatera
"dreamedup" the Schriidinger equationcan be had by exan-rir.ring tirre and
thc
spatialdepcndence thatcharacterizes so-called travelingu,aves. lt shouldbe noted
that the peoplervhoworkedon theseproblcmskneu'a greatdcal aboutu'aves
(e.g.,soundw'avesand \\.ater\\'aves)and thc equationsthey obeyed.Moreover.
they kneu' that u,avescould sometimesdisplaythe characteristic of quantized
u'avelenqths or fi'equencies (e.9..fundamentals and overtonesin soundu'a'"'es).
They'kneu',for example.that r.r,a'u'esin one dinrensionthat are constrainedat trvo
points(e.g..a violin stringheld fixed at tu'o ends)undergooscillatorymotjon
in spaceandtime with characteristic fi'equencies andu'avelengths. For exan.rple.
the motion of the violin stringjust nrentionedcan be describedas havingan
arnplitudeA(r. t ) at a position-r alon-qits len-sthat tinle I gircn by
l ( , 1 -/ .) : , 4 ( . r - . 0 ) c o s ( 2 . ' r y r ) . (1.13)
where r, is its oscillationfrequency.The arnplitude'sspatialdependence

alsohas
a sinusoidaldependence givenby
I (,r.0) : A sin(2r:;l).1. (1.1.1)
where.),is the crest-to-crest

lengthof the rvave.Two examplesof suchwaves1n
onedimensionareshownin Fig. 1.4. In thesecases,the stringis fixedat x : 0 and
at x : l, so the $,avelengthsbelongingto the two wavesshownare ), : 2L and
),= L.lf the violin string were not clarnpedat ir: I, the wavescouid have
any value of ),. Horvever.becausethe string is attachedat ir : l. the allowed
u'avelengthsare quantizedto obey
)"= Lln. (1.15)

sin(hx/LJ
w h e r en : 1 . 2 , 3 . 4 , . . . T h e equation
t h a t s u c hw a v e so b e y ,c a l l e dt h e w a v e
F u n d a m e n t aaln d f i r s t equation.reads
overtone notes of a
d2,4(x,t) . d2A
v i o l i ns t r i n g . (r . l 6 )
Lll- (l\-
W h y q u a n t u mm e c h a n i c si s n e c e s s a r fyo r d e s c r i b i n gm o l e c u l a rp r o p e r t i e s
wherec is the speedat which the wavetravels.This speeddependson the com-

positionof the materialfrom which the violin string is made.Using the earlier
expressions for the -r- and t-dependences
of the wave,A(x,t). we find that the
rvaves frequencyandwavelengtharerelatedby the so-calleddispersionequation:
v : : ( c l n ) :. (r .r 7 )
or
c: tv. (1.18)
This relationshipimplies,for example.that an instrumentstring made of a very

stiff material(largec) will producea higherfrequencytonefor a givenwavelength
(i.e.,a givenvalueof n) thanwill a stringmadeof a softermaterial(smallerc).
For waves moving on the surface of, for example. a rectaneulartwo-
dimensionalsurfaceof lengthsI,, and 1,,, one finds
l(.r. r. /) = sinln,:rr I L.,)sin(n,:ry

I L, )cos(2zur) (1.19)
Hence.the wavesare quantizedin two dimensionsbecausetheir wavelengths

mustbe constrained to cause,4(x.y. r) to vanishat_r : 0 and-r : Z. aswell as
at -r,- 0 and,y : I,, for all times t. Let us now return to the issueof wavesthat
describeelectronsmoving.
The pioneersof quantummechanicsexaminedfunctionalforms similar to
thoseshownabove.Forexample,fbrmssuchas I : exp[*22 i( ur - .y/i)] were
consideredbecausetheycorrespondto periodicwavesthat evolvein -vanclt under
no external,t'-or l-dependentforces.Noticing that
Jt.J /22 \r
;(/.\-
- : - l . l l (1.20)
\ ,\ ,/
andusingthe de Brogliehypothesis
X: hlp in the aboveequation.one finds
,l:.1 .71.2 \l
-:-p-l , | ,a (r.21)
.1.\'- \ tt /
If I is supposedto relateto the motionof a particleof momentump underno

externaltbrces(sincethe waveformcorrespondsto this case),p2 canbe related
to the energy E of the particle by E : p212m. So, the equationfor I can be
rewrlttenas
'ti1= -2,,r('* ,,.

(1.\'- n
)' \ /
(1.22)
or, aiternatively.
-(*)'#: uo r t 1l\
10 T h e b a s i c so f q u a n t u mm e c h a n i c s
Returningto the time-dependence

of l(.r'. /) and using v : Elh. one can also
show that
/ h \ dA
i ( ^ I ' : E i t ' (1.24)
\tlr / dl
which, using the first result.suggeststhat
th 1d.4 r lt \:J:A
'\=/ :- (1.2s)
,t, \;/ ,..
This is a primitiveform of the Schrcidinger

equationthatwe rvill addressin much
more detail below.Briefly, what is importantto keep in mind is that the use of
the de BroglieandPlanclCEinstein connectionse,: h/p an<iE : lr,), bothof
which involvethe constanti. producessuggestive connectionsbetrveen
,(+)# and
E (r . 2 6 )
and bet."veen
r , 1/t1:d:
D- anc ( 1 . 2| 7
\ 2:r) dt:
or, alternatively.between
7.' and - , (:-'\ +

\ :1T / .1.\
(1.18)
Theseconnectionsbetweenphl,sicalproperties(energyf and mornentump)and

differentialoperatorsare someofthe unusualfeaturesofquantum mechanics.
The abovediscussionabout wavesand quantizedu,avelengths as rvell as the
obser"'ationsabout the wave equationand differentialoperatorsare not meant
to provide or even suggesra derivationof the Schrodin_eer equation.Again the
scientistswho inventedquantummechanicsdid not deriveits rvorkingequations.
Insteadthe equationsand rules ofquantum mechanicshavebeenpostulatedand
designedto be consistentu'ith laboratoryobservations.My studentsoften find
this to be disconcertingbecausethey arehopingand searchingfor an underlying
fundamentalbasisfrom vvhichthe basiclarvsof quantummechanicsfollou, log-
icall1,.I try to remind them that this is not hou' theory u,orks.lnstead.one uses
experimentalobservationto postulatea rule or equationor theory,.and one then
teststhe theory by making predictionsthat can be testedby further experiments.
Ifthe theory fails, it must be "refined", and this processcontinuesuntil one has
a betterand bettertheory.In this sense.quantummechanics,with all of its un-
usual mathematicalconstructsand rules. shouldbe viewed as arising from the
imaginationsof scientistswho tried to invent a theory that was consistentwith
experimentaldataand which could be usedto predict thingsthat could then be
testedin the laboratory.Thus far, this theory hasprovenreliable,but, of course,
T h e S c h r o d i n g eer q u a t i o na n d i t s c o m p o n e n t s t l
"new and improved"

we are ahvayssearchingfor a theory that describeshow
smalllightparticlesmove.
If it helpsyou to be more acceptingof quantumtheory,I shouldpoint out
that the quantLrm descriptionof particleswill reduceto the classicalNewton
description undercertaincircumstances. In particular,when treatingheavypar-
ticles(e.g.,macroscopic massesand evenheavieratoms),it is oftenpossibleto
useNer,vtondynamics.Briefly. rve will discussin more detail how the quantum
and classicaldynamicssometimescoincide(in which caseone is free to use
the simpler Neu,tondvnamics).So. let us now move on to look at this strar.rge
Schrodinger equationthat lve havebeendi-eressingaboutfor so long.
1.2 The Schrodingerequationand its components

It hasbeenwell established that electronsmoving in atomsand moleculesdo
not obeytheclassicalNewtonequations of motion.Peoplelong agotriedto treat
electronicnlotionclassicallv. and tbundthat featuresobservedclearlyin erperi-
mentalmcasurements simplywerenotconsistent with sucha treatment. Attentpts
r,veremadeto supplcrnent the classicaleqr-rartions rvith conditionsthat could be
usedto rationalizesuchobservations. For eraniple.earlvrvorkersrequiredthat
theangularmomentllmL : r x p be allowedto assumeclnl,vintegermultiplesof
l/22 (lvhichis ofien abbrcviated as fi), which can be shorvnto be cquivalenr to
the Bohrpostulatetti : 2:rr. Hor,vever. until scientistsrealizecl
thata ner',,
setof
lar.ls.thoseof cluantum rlechanics.appliedto light rnicroscopic particles.a rvide
gullexistedbetr.leen laboratoryobserlationsof molecule-lcvel phenomena and
thc equations uscdto describesuchbehavior.
Quanturnrnechanics is castin a languasethat is not farniliarto moststudents
of chemistryrvhoare exarrininsthe subjectfbr the first timc-.Its nrathernatical
contentandhorvit relatcsto experimental measurements bothrecluirea -grc-at
deal
of eftortto mastcr.With thesethoughtsin mind.I haveorganizedthis ntaterialin
a mannerthatfirst providesa brief introductionto the two prirnaryconstructs of
qLlantum mechanics operators andwavefunctionsthatobeya Schrodinger equa-
tion.Next.I dcmonstratc theapplication of theseconstructs to severalchemically
relevantmodelproblents.By learningthe solutionsof the Schrodinger eqLlatlon
fbr a f'ewmodel systems,the str"rdent can betterappreciatethe treatmentof the
fundamental postulates of quantummechanics as well astheirrelationto experi-
mentalrreasurement for whichthewavefunctionsof theknolvnmodeloroblems
off!r inrportuntinrerpr,.'rations.
1. 2 . 1 O o e r a t o r s
E a c hp h y s i c a l l ym e a s u r a b l eq u a n t i t yh a s a c o r r e s p o n d i n go p e r a t o rT, h e
e i g e n v a l u eosf t h e o p e r a t o tre l lt h e o n l y v a l u e so f t h e c o r r e s p o n d i n pg h y s -
ical propertythat can be observed.
Any experimentallymeasurablephysicalquantityF (e.g.,energy.

dipole mo_
ment.orbitalangularmomentum.spin angularmomentum,
linearmomentum,
kineticenergy)hasa classicalmechanicar expression in termsof thecartesianpo_
sitions{q;} andmomenta{p; } of theparticlesthatcomprisethe
systemof interest.
Eachsuchclassicalexpression is assigned
a correspondins quantummechanical
operatorF formed by replacingthe lp1) in the classicalform
by the differentiar
operaror-i/1 0/0q 1ar.rd reavingthe coordinates97 that appearin F untouched.
Forexample.the classicar kineticenergyof y'y'
particles(u,ithmasses r?1)movlnir
in a potentialfield containingboth quadraticand rinear
coordinate-def"nd.n.e
can be written as
r:,I, + t, ( q,- q) ,) l
t/2k( q1- ,tl) (1.29)
l t'i /2u ,,+
The quanturnmechanicaloperatorassociatedwith this
.F is
t :,I, - +t'(q,-'ti')]
L*,# * )r (,' q;')' (I . 3 0 )
Suchan operatorwould occurwhen,for example,one

describes the sum of'the
kineticenergies of a collectionof particles(the
f,:, ,,(7ti/2,,11rerm).plus rhe
sum of "Hooke'sLavu'''parabolic potentialstthe lfZy,,=t.t k(qr _ q!t'721, ana
(the last term in F) the interactionsof the particles
*itn ln .*r.rnaily appried
field whosepotentiarenergyvarieslinearryasthe particles
moveaivayfrom their
equilibriumpositions{4,0}.
Let us try more exampres. The sum of the:-components of angularmomenta
(recallthat vectorangurarmomenfurnL is defined
as L : r x p; ota collection
of ly' particleshas the following classicalexpression:
t: GiPvt-)'tP,i), (r.31.)
f
-/= I ..'\'
and the correspondingoperatoris
t : -t,.,:.Iu
(',* - r',+) ( r. 3 2 )
If one transformsthesecartesiancoordinatesand
deri'ativesinto polar coordi_
nates,the aboveexpressionreducesto
a
F--iltf ( 1. 3 3 )
i?' 3Qi
The r--componentof the dipole moment for
a coilection of 1y'particleshas a
classicalform of
'p -- ./--
\- Z1exi, ( r.34)
T h e S c h r o d i n g eer q u a t i o na n d i t s c o m p o n e n t s 12
for which the quantttmoperatoris
F: I Z,exi, (r .3s)
*'here Z 1e is the chargeon theTthparticle.Notice that in this case,classicaland

quantumforms are identicalbecause-F containsno momentumoperators.
The mappingfrom F to F is straightforwardonly in termsof Cartesiancoor-
dinates.To map a classicalfunction .E,given in termsof curvilinearcoordinates
(evenifthev are orthogonal),into its quantumoperatoris not at all straightfor-
ward. The mappingcan alwaysbe done in terrnsof Cartesiancoordinatesafter
which a transtbrmationof the resultingcoordinatesand differentialoperatorsto
a curvilinearsystemcan be performed.
The relationship of thesequantummechanical operators
to experimental
mea-
surementlies in the eigenvaluesof the quantumoperators.Each such operator
h a sa c o r r e s p o n d i negi g e n v a l ueeq u a t i o n
F x ,: u , x , (r . 3 6 )
in which the X7 arecalledeigenfunctions andthe (scalarnumbers)cv;arecalled

eigenvalues. All sucheigenvalue equations areposedin termsof a givenoperator
(F in this case)and thosefunctions{X/} that F actson to producethe function
back againbLrtmultipliedbv a constant(the eigenvalue). Becausethe operator
F usuallircontainsdifferentialoperators (coming from the momentum).these
equations aredifferentialequations. TheirsolutionsX, dependon thecoordinates
thatF containsasdiflerentialoperators. An examplewill helpclarif,vthesepoints.
The differcntialoperatord f d.r' actson rvhatfunctions(of_r,)to generatethe same
functionbackagainbut multipliedby a constant? The answeris functionsof the
form exp(rl-r,)
since
(1.37)
So. we saythat exp(a_r,) is an ei-eenfunctionof d ldy and a is the corresponding

eigenvalue.
As I will discussin moredetailshortly,theeigenvalues of theoperatorF tell us
the onlt,valuesofthe physicalpropertycorrespondingto the operatorF that can
be observedin a laboratorymeasurement. SomeF operatorsthat we encounter
possess eigenvalues that arediscreteor quantized.Forsuchproperties.laboratory
measurement will result in only those discretevalues.Other F operatorshave
eigenvalues that can take on a continuousrangeof values;for theseproperties,
laboratorymeasurement can give any value in this continuousrange.
1 . 2 . 2W a v ef u n c t i o n s
The eigenfunctiono s f a q u a n t u m m e c h a n i c aol p e r a t o rd e p e n d o n t h e
coordinatesupon which the operator acts. The particularoperator that
c o r r e s p o n d st o t h e t o t a l e n e r g yo f t h e s y s t e mi s c a l l e dt h e H a m i l t o n i a n
operator.The eigenfunctionsof this particularoperator are called wave
functions.
A specialcaseofan operatorcorresponding to a phvsicalll,nreasurable quan-

titv is the HamiltonianoperatorH that relatesto the total enercyof the system.
The energyeigenstates ofthe svstemW are functionsofthe coordinates1g;1
t h a t H d e p e n d so n a n d o f t i m e l . T h e f u n c t i o ni V ( r 7 ; . 1 ) l l : W - V g i v e st h e
probabilitydensitvfor observingthe coordinates at the valuesq; at tirnel. For
a manv-particle systemsuchas the H2o molecule"the u'avefunctiondepends
o n m a n yc o o r d i n a t e F
s .o r H 2 O .i t d e p e n d o
s n t h e . x . . r .a
. n d : ( o r r . 0 . a n dS 1
coordinates of thetenelectronsandthe.r-..r,.and: (or r. 0. and(t) coordinates oi'
theoxygennucleusandofthe two protons;a totalof39 coordinates appearin v.
ln classicalmechanics. the coordinatcs q7 and their correspondins momenta
p.i arefunctionsof tinre.The stateof the systemis thendescribed bl,spccifvine
q j(l) andp 1(tl.In quantumntechanics.theconceptthat17;is knor,"'n asa funr:tion
of tirneis replacedby the conceptof the probabilitvdcnsitvfor 1indingQi ar ?
particular"'alueat a particulartime lv(r7r. t)lr. Knorvledge of thc corresponding
momentaas functionsof time is alsorelinquished in quantumnrechanics: lgain.
onlyknou'ledge of theprobabilitvdensiryfor finding7r, r.vithanyparticularr,,aluc
at a particulartime / remarns.
The Hamiltonianeigcnstates are especiallyirnportantin chenristrybecause
manyof thetoolsthatchemistsuseto studymoleculesprobetheenergystatesof
themolecule.Forexample, nrostspectroscopic methodsaredcsigned to deterrnine
u,hichenergystatea moleculeis in. However.thereareotherexperimental melh-
odsthatmeasureotherproperties(e.g.,the :-cornponentof angularmonrentun.r
or the total angularmomentum).
As statedearlier,if the stateof somemolecularsvstemis characterized b1'a
wavefunctionw that happensto be an eigenfunction of a quanlummechanical
operatorF, one can immediatelysay somethingabout what the outcome $,ill
be if the physicalproperty F correspondingto the operatorF is measured.In
particular,sir.rce
Fxt : )",x1. (r . 3 8 )
wherei 7 is oneof theeigenvalues of F. we know thatthevaluei7 wili be observed
if thepropertyF is measuredwhile thernoleculeis describedby thervavefuncrion
'4t:
X.i.ln fact,oncea measurement of a physicalquantityF hasbeencarried
out and a particulareigenvalue).i hasbeenobserved-the system'srvavefuncrion
v becomesthe eigenfunction1, that correspondsto that eigenvalue. That is, the
T h e S c h r o d i n g eer q u a t i o na n d i t s c o m p o n e n t s 15
actof makingthe measurement causes the system'swavefunctionto becomethe

eigenfunction of the propertythat tvasmeasured
What happensif someotherpropertyG, r.vhose quantummechanicaloperator
is G is measuredin sucha case?We knou' from what was said earlierthar some
ei_genvaltrepr of the operatorGlvill be observedin the measurement. But. will
the molecr-rleiwavefunctionrenrain,after G is measuredthe eigenfunction of
F, or will the measurement of G causeV to be alteredin a way that makesthe
molecule'sstateno longeran eigenfunction of F? It turns out that if the two
operatorsF and G obey the condition
F G = G F (1.39)
then.when the propertyG is measuredthe wavefunction'Q : Xtrvili remain

unchanged. This propertv.thattheorderofapplicationofthe two operators
does
not matter.is calledcontmutation:that is, we savthe tu,ooperatorscommuteif
theyobeythispropertv.Let us seehowthispropertyleadsto theconclusionabout
V remainingunchangedif the tr,vooperatorscomnlute.In particulaqwe apply
theG operatorto the aboveeigenvalue equation:
C F 7 . ,: G 1 i Xi . ( r. .10)
Next.rveusethe comntutation to re-writcthe leti-handsideof this equation.and
u s et h e f a c tt h a ti , i s a s c a i a n
r u r n b e r t ot h u so b t a l n
F G7i: r.Q7, (1.-1lt
So. nor.vwe scc that (G;1,) itself is an ei-uenfunctionof F havingeigenvalue

ir. So, unlessthereare l.norethan one eigenfirnctions of F corresponding to
i; (i.c..unlessthis cigenvalue
the eigenr.aluc is degenerate).GX, n.rustitselfbe
proportionalto 21r.We write this proportionalirv conclusionas
GX,: ltix,. (1.:12)
which meansthat X, is also an eigenfunctionof G. This. in turn. meansthat

measuringthe propertyG rvhilethe systemis describedby the wave function
tp :
X i d o e sn o t c h a n g et h ew a v et u n c t i o ni:t r e m a i n sX , .
So. lvhenthe operatorscorresponding to two physicalpropertiescommLlre,
once one measures one of the properties(and tlius causesthe systemto be an
eigenfunction ofthat operator).subsequent measurcment ofthe secondoperator
will (iithe eigenvalue of the first operatoris not degenerate) producea uniqtLe
eigenvalue ofthe secondoperatorandwill not changethe systemwavefunction.
If the two operatorsdo not commute.one simply can not reachthe above
conclusions. In suchcases.measurement of the propertycorresponding to the
first operatorrvill leadto one ofthe eigenvalues ofthat operatorand causethe
system lvave function to become the correspondingeigenfunction.However,
to T h e b a s i c so f q u a n t u mm e c h a n i c s
subsequent measurementof the secondoperatoru'ill producean eigenvalueof

that operator.but the systemu'avefunction will be changedto beconrean crgen-
functionofthe secondoperatorand thusno longerthe eigenfunction ofthe first.
1 . 2 . 3T h e S c h r o d i n g eerq u a t i o n
T h i s e q u a t i o ni s a n e i g e n v a l u ee q u a t i o nf o r t h e e n e r g yo r H a m i l t o n i a n
operator;its eigenvaluesprovide the only allowed energy levels of the
sysrem.
The ti me-depe n dent eq u ati o n

l f t h e H a m i l t o n i a no p e r a t o rc o n t a i n st h e t i m e v a r i a b l ee x p l i c i t l yo, n e m u s t
solvethe time-dependentSchrodingerequation.
Beforemovingdeeperinto understanding whatquantummechanics "means".

it is useful to learn horv the wave functions V are found by applying the ba-
sic equationof quantun.r mechanics. the Schrodinger equation.to a few exactly
solublemodelproblems.Knorvingthe solutionsto these"easy"vet chernically
very relevantmodelsr.l,illthen facilitatelearninsmore of the detailsaboutthe
structureof quantummechanics.
The Schrodinger equationis a differentialequationdepending on tirneandon
all ofthe spatialcoordinates necessarl,to describerhesystemat hand(thirt1,-nine
for the H2O examplecited above).lt is usuallyn,ritten
H t U : i 7 16 r y 1 ' 6 , . (1.43)
wherev(qi, t.) is the unknownwave function and H is the operatorcorrespond-

ing to the total energyof the system.This operatoris called tl.reHar.niltonian
and is formed, as statedabove,by first writing down the classicalmechanical
expressionfor the total energy(kinetic plus potential)in Cartesiancoordinates
and momenta and then replacingall classicalmomentap; by their quantum
mechanicaloperatorsp j : -ih 0lSq.i.
FortheH2o exampleusedabove,theclassicalmechanicalenergyof all thirteen
particlesis
F _ s.Ip; l/r\-e -\-2,"'t

+ l r ^ - 't - /_J t.t.t ? ,," I
- r+- fl pr j* -r-' -r 'ir- \-? Z'Zr'i

ruh
I ( r.44)
I'
wherethe indicesi andj are usedto label the l0 electronswhose30 Cartesian
coordinatesarelq il anda and b labelthe threenucleiu,hosechargesaredenoted
{Zo}, and whosenine cartesiancoordinatesare lqo}. The electronand nuclear
T h e S c h r o d i n g eer q u a t i o na n d i t s c o m p o n e n t s
17
massesare denotedrr. and {n,,}, respectively.The correspondingHamiltonian

operatoris
H=E
* #l . : l * - + T l
.+[-*#.:+'#l .'15)
NoticethatH is a secondorderdifferentialoperatorin thespaceofthe 39 Cartesian
coordinatesthat describethe positionsofrhe ren electronsand threenuclei.lt is
a secondorder operatorbecausethe momentaappearin the kinetic energyas pr2
andp;,and the quantummechanicaloperatorfor eachmomentump : _ f ttl 0q
I
is of first order.TheSchrodingerequationfor the H2o example at hand then
reads:
't7 l-Ai- - 1\- "' - \- Z,e:w

1 2n,dq; ??r,, ?,.,"
-tl_ l a: ;l r!
'll2n,'dq.; * 1 l Z , Z n e :\ y : ln- ( 1.16)
2? rr.h At
The Hamiltonianin this casecontains/ nowhere.An exampleof a casewhere11

doescontain/ occurswhenan oscillatingelectricfield E cos(ror)alongthe-r-axrs
interactswith the electronsand nuclei and a term
)- f
Z,rX,,f.cos((r/ e;r7E
cos(rr-rr) (1.47)
)
is addedto the Hamiltonian.Here,xo and.,videnotethe.r coordinatesof the
ath
nucleusand the7th electron.respectivelv.
The ti me-i ndepe ndent eq uatio n
lf the Hamiltonianoperator does not containthe time variableexplicitly,

one can solve the time-independentSchrodingerequation.
In caseswherethe classicalenergy,and hencethe quantumHamiltonian,

do
not contarntermsthatareexplicitlyrimedependent (e.g..interactions with time
varying externalelectric or magneticfields rvould add to the above
classical
energyexpressiontime dependentterms),the separations of variablestechniques
can be usedto reducethe Schrodingerequationto a time-independent
equation.
In suchcases,H is not explicitlytime dependent, so one can assumethat
v (.qi ' t ) is of the form (n.b.,this stepis an exampleof the useof the
separations
of variablesmethodto solvea differentialequation)
V ( q , , t ) = W ( qi ) F ( t ) (l.4E)
this "ansatz"into the tir.ne-dependent

Substituting equationgives
Schrodin_ser
V ( q 1 )i t t 0 F l ' d t: F Q ) H V ( qt t . (1.49)
D i v i d i n gb y V ( q 1 1 F ( tt)h e ng i v e s
F t t i ht ) F l i t r t : W i [ H , ! ( 4)i] . (1.50)
SinceF(l ) is only a functionof time t. andtU(q 1)is only a functionof the spatial
coordinates lq 1], andbecausethe left-handand riglit-handsidesmust be equal
for all valuesof t and of lq il, both the left- and right-handsidesmust equala
constant. lf this constantis calledE. the two equationsthatareernbodiedin this
separatedSchrodingerequationreadas follou,s:
HV(q,): EV(q,). ( l . 5 l)
ifidF(t)ldt: EF(t). il.sl)
Thefirstoftheseequations is calledthetin-re-independent Sclrrodinger equatron: it
is a so-called eigenr,alue equationin u'hichoneis askedto find functionsthat1,ield
a constantmultipleof ther.nselves when actedon by the Hamillonianoperator.
Suchfunctionsarecalledeigenfunctions ofH andthecorresponding coustallts are
c a l l e dc i g . e n r a l u oe fsH . F o re x a m p l ei .f H u e r eo f ' r h ef o r m ( _ l i ' 2 . \ lt ; t :, d Q : -
H" tlrenfunctionsof thc form exp(inrQ)would be eigenfunctions because
I li d: I ln:h:l
,-
- - l
ztra6,1e x p ( i', , i @ ) : l * f crptiirrd,). ll.-i.l)
I [:,r,J
In thiscase.rr 2tt2
12tvtis theeigenvalue. In thisexample.theHarriltoniancontains
the squareof an angularmomentumoperator(recall earlierthat u,'eshou'edtlre
:-cornponent of angularmomentumis to equal-ih d ldQ).
\Vhen the Schrcidingerequation can be separatedto -seneratea time-
independent equationdescribingthe spatialcoordinatedependence ofthe u'ave
function,the ei_eenvalue E mustbe retumedto the equationdeterminingF(t) to
find the time-dependent part of the wavefunction.By solving
ifldF(r)ldt: EF(t) (1.54)
once E is known.oneobtains
F(t) = gapl-i E1171, (1.55)
and the full wave function can be written as
v ( qi . r ) : w ( q i )e x p ( -i E t l t t ) . (1.56)
For the aboveexample,the time dependence

is erpressedby
F(r) : exp(-irlnt2ti1zll1itt1. (l . s 7 )
T h e S c h r o d i n g eer q u a t i o na n d i t s c o m p o n e n r s
tv
In summary,wheneverthe Hamiltoniandoes not dependon time explicitly,

one can solvethe time-independent Schrodinger equationfirst and thenobtain
rhetime dependence as exp(-i El/fi) oncethe energyE is known. In the case
of rnolecularstructuretheory,it is a quite dauntingtask even to approximately
soivethe full Schrodinger equationbecauseit is a partialdifferentialequarion
dependingon all of the coordinates of the electronsand nucleiin the molecule.
For this reason.there are various approximationsthat one usually implements
when attemptingto study molecularstructurer.rsingquantummechanics.
The Born-O ppen hei me r approxi m ati on

one of the mostimportantapproximationsrelatingto applyingquantummechan-
ics to moleculesis knownas the Born-oppenheimer(Bo) approximation. The
basicideabehindthis approximationinvolr.esrealizingthatin the full electrons-
plus-nucleiHamiltonianoperatorintroducedabove,
H : t l - , iz n tri t'q--: l \ - - " ' - ' t a l

?1 2?'',, ?,,"1
7 7 . :
*,-l_fir;rr_l \..-
z!/ zxc
(r . 5 8 )
" 2nr,,;)q,] 2 ';
t'u.h
|
the tirne scalesivith which the electronsand nuclei move are generallyquite
difl'erent.In particular.the heavynuclei(i.e.,evena H nucleusweighsnearly
2000timeswhatan electronweighs)move(i.e.,vibrateandrotate)moreslowly
thando the lirrhterelectrons. Thus.r','cexpectthe electronsto be ableto ..adjust,'
theirmotionsto themuchrrroreslowlymo'n,ing nuclei.Thisobservationmotivates
r.rsto solvethe Schrcidingerequationtbr the movementof the electronsin the
presenceof fixed nuclei as a vvilvro representthe fully adjustedsrateof the
electronsat any fixedpositionsofthe nuclei.
The electronicHamiltonianthatpertainsto the motionsof theelectronsin the
presence of so-calledclarnpednuclei.
H : -\ - l - l r 't ti, ": t -, 1*: 1 t ' ' ' - r'Z{

t/ l (1.59)
I )L,"., ,,, l'
producesas its eigenvalues.
throughthe equation
H O 1 ( q1 i r l , ) : E r k l , , ) , ! . t ( q I, q , ) . (1.60)
energresErGl,) that dependon where the nuclei are located(i.e., the
{r7,,}
coordinates).As its eigenfunctions. one obtainswhat arecalledelectronicwave
functionsltLrkti I r7,,))which alsodependon wherethe nucleiarelocated.The
energiesE xQ") arewhatwe usuallycall potentialenergysurfaces. An example
of sucha surlaceis shoivnin Fig. 1.5.This surfacedependson two geometrical
coordinates{r7,,}a'd is a plot of one particulareigenvalue
EL@,) vs. thesetwo
coordinates.
Secondorder saddlePotnl
fransrtion structureA
Minimum for
product A
- 0.,5
Two-dimensional Secondorder n
saddlepoint
potentialenergysurface
\ralley-ridgc
s h o w i n gl o c a lm i n i m a , 0.5
i n f l e c t i o np o t n t
transitionstatesand Minimum for reactant
p a t h sc o n n e c t i n g
them.
Although this plot has more information on it than we shall discussnou'.

a few featuresare worth noting.Thereappearto be tlireeminima (i.e..points
of -87 rvith respectto both coordinatesvanishand u'here
r,l,herethe derir"atives
the surfacehas positivecurvature).Thesepoints correspond"as we u'ill seeto-
u,ard the end of this introductorymaterial,to geometriesof stablet.nolecular
(labeledtran-
structures.The surfacealso displaystwo first order saddlepoints
sition structuresA and B) that connectthe three mininra. Thesepoints havezero
first derivativeof E.r with respectto both coordinatesbut have one direction
of negativecurvature.As we will show later, these points describetransition
statesthat play crucial roles in the kineticsof transitionsamongthe three stable
geometries.
Keep in mind that Fig. 1.5showsjust one of the tJ surfaces;eachmolecule
has a ground-statesurface(i.e., the one that is lowest in energ.v)as well as an
infinitenumberofexcited-statesurfaces.Let'snou'returnto our discussionofthe
BO model and ask what one doesonceone has suchan energysurfacein hand.
The motions of the nuclei are subsequently,within the^Bo model. as-
sumed to obey a Schrodingerequationin u'hich L"{-(h'l2nt,,)d!l\q;-l
1l2l,n ZoZ6e2f ro.6]* E r@) definesa rotation-vibrationHarniltonianfor the
particularenergystateE5 ofinterest.The rotationalandI'ibrationalenergiesand
wave functionsbelongingto eachelectronicstate(i.e., for eachvalue of the in-
dex K in E x@)) arethen found by solving a Schrodingerequationrvith sucha
Hamiltonian.
This BO model forms the basis of much of how chemistsview tnolecular
For exarnple,as appliedto forrraldehyde
structureand rnolecularspectroscopy.
H2C:O, we speakof the singletgroundelectronicstate(with all electronsspin
paired and occupyingthe lowest energyorbitals) and its vibrational statesas
M o t i o n o f a p a r t i c l ei n o n e d i m e n s i o n 21
nell as the n --+ z* and ir --->lr*electronicstatesand their vibrationallevels.

Althoughmuch more will be said about theseconceptslater in this text. the
studentshould be arvareof the conceptsof electronicenergysurfaces(i.e.. the
lExe,)]) and the vibration-rotarion statesthatbelongro eachsuchsurface.
Having been introducedto the conceptsof operators,wave functions.the
Hamiltonianandits schrodin-eer equation,it is importantto now considerseveral
examplesof the applicationsof theseconcepts.The examplestreatedbelorvwere
chosento providethereaderwith vaiuableexperience in solvingtheSchrodinger
equation:they werealsochosenbecausethey form the n]ostelementarychemical
modelsof electronicmotionsin conjugated moleculesand in atoms,rotationsof
linearmolecules,and vibrationsof chemicalbonds.
1.3 Yourfirst applicationof quantum mechanics- motion

of a particlein one dimension
This is a very important problem whose solutionschemistsuse to model
a wide variety of phenomena.
Let's begin by examiningthe motion of a singleparticleof mass,n ln one

directionwhich rvewill call "r rvhiler-rnder the influenceof a potentialdenoterl
Z(,r). The classicalexpressionfor the total energyof such a systemis .E :
p212n -t V(x), rvherep is the momentumof the particlealong ther-axis. To
focuson specificexamples, considerhorvthis particlewould moveif I/(.r.1il'ere
of the forms shor.vnin Fig. I .6. wherethe total energyE is denotedby theposition
ofthe horizontalline.
1 . 3 . 1C l a s s i c aplr o b a b i l i tdy e n s i t y
I would like you to imaginewhattheprobabilitydensitywould be for this particle
moving with total energyE and with I/(,r) varying as the threeplots in Fig. L6
Three
characteristic potentials
showing left and right
c l a s s i c at lu r n i n gp o i n t s
at energiesdenotedby
t h e h o r i z o n t aIli n e s .
illustrate.To conceptualize theprobabilitydensitl'.imaginethe particleto havea

blinkinglan.rpattached to it andthink of this lampblinkingsay100timesftrreach
time intervalit takesfor theparticleto completea full transitfrom its lefi turning
point to its right turning point and back to the former.The turning points,r-sand
-rRarethe positionsat whichtheparticle,if it weremo'"'ing underNe\\'ton'siau's.
wouldreversedirection(asthe momentumchangessign)andturn around.These
positionscan be found by askingwherethe momentumgoesto zero:
0 : p : ( 2 m ( E - I ' ( . t ) )r r. (1.6i)
Thesearethe positionsrvhereall ofthe energyappearsas potentialenergvE :

I/(.x) and correspondin the abovefiguresto the pointsrvherethe dark horlzontal
linestouchthe I'(r)plots as sho'uvn in the centralplot.
The probabilitydensityat any valueof -r:represents the fractionof'tirllethe
particlespendsat this valueof (i.e..
..r- u'ithin.r and,t * r/.r).Think of forrrling
this density'by allowingthe blinking lantpattachcdto the particleto shedlight
on a photo-eraphic plate that is exposedto tliis light for many oscillationso1-
the particlebet\\'een -r1 and;rp. Alternatively.one can expressthis probability
amplitude P(r) by dividingthe spatialdistancer/.r"by thevelocitl'of theparticle
at tlie nointr:
I r r r rr i r
P ( - t ): ( 2 m ( E - I " ( . r) ) (i.62)
BecauseE is constantthroughoutthe particle'smotion.P(,t)tl'ill be smallat,t

valuesu,heretheparticleis mo'u'ingquickly (i.e..'ui'here
l/ is lou') andri'ill be high
wherethe particlemovesslowly 1r,r,here tr/is high). So. the photographic plate
u'ill shou,a brightregionwhere I/ is high (because the particlemovesslou'lyin
suchregions)and lessbrightnesswhere tr' is lou'.
by analyzingthe
The bottomline is thatthe probabilitydensitiesanticipated
classicalNewtoniandynamicsof this oneparticle'uvould appearasthehistogran.r
plotsshownin Fig. 1.7 illustrate.Wheretheparticlehashighkineticenergy(and
thuslower Z(.lr)),it spendslesstime and P(.t) is small.Wheretheparticlemoves
Classical
ty plotsfor the
three potentialsshown
i n F i g .1 . 6 .
M o t i o no f a p a r t i c l ei n o n e d i m e n s i o n 23
slorvly.it spendsmore time and P(.r) is larger.For the plot on the ri_eht,/(,r)
"box".
is constantwithin the so the speedis constant.hencep(.r) is constant
fLrrall .v valuesrvithinthis one-dimensionalbox. I ask that you keepthesepiots
in nrind becausethey are very difrerentfrom what one finds when one solves
the Schrcidinger equationfor this sameproblem.Also pleasekeepin mind that
these plots representwhat one expectsif the particle were moving accordingto
classicalNewtoniandynamics(w,hichwe know it is notl).
1 . 3 . 2O u a n t u mt r e a t m e n t
To solve tbr the quantLlmmechanicalwavefunctionsand energiesof this same
problem,we first write the Hamiltonianoperatoras discussedaboveby replacing
n Ov -lll(l /Ll.\".
h' ,t:
Il:-'--l+l'rrr (1.63)
lilt tl.\-
We then try to find solutionsry'(.r)to Hrlr : ErL that obey certainconditions.

Theseconditionsare relatedro the fact that iry'(.r)12 is supposed to be the prob-
ability densityfbr findinethe particlebetrveen -r and.r * r/.r.To keepthingsas
simpleas possible,let'sfocuson the "box" potential/ shorvnin the right side
o f F i g . 1 . 7 .T h i sp o t e n t i a le. x p r e s s eadsa f u n c t i o no f , r i s : V ( x \ : c c f o r - r < 0
andfbr,r > L: I/1.r1: 0 fbr.r-between0 and l.
The factthat tr/is infinitefor-r < 0 andfor.r > l. andthatthe totalenergyE
mustbe finite.saltsthat /r mustvanishin thesetwo regionsdt : 0 for_r < 0 and
forx > l). This conditionmeansthat the particlecan not accessthesereslons
wherethe potentialis infinite.Thc secondconditionthat.nve makeuseof is that
/(-t ) mustbe continuous: thisrrreans thatrheprobabilityof theparticlebeingrt,r
cannot be discontinuously relatedto theprobabilityofit beingat a nearbypornr.
1 . 3 . 3E n e r g i e sa n d w a v e f u n c t i o n s
The secondorderdift-erential
equation
il tlllr
- -;-. -t tr/\r)tlr : Etlt (1.6.+)
^
lnt dr'
hastwo solutions(becar.rse
it is a secondorderequation)in the regionbetrveen
"r:0andx:L:
/ : s i n ( l . r ) a n d r y :' c o s ( , t - r ) . r v h e r e A i s d e f i n e dka :s( 2 m E l t t : 1 | i 1 . ( 1 . 6 5 )
Hence.the mostgeneralsolutionis somecombinationof thesetrvo:
ty': .1sintA.r)
+ B cosrfr.r'.y. (1.66)
z4 T h e b a s i c so f q u a n t u mm e c h a n i c s
T h e f a c t t h a t r y ' m u s t v a n i s h a t , v : 0 t n . b . . r / r v a n i s h e s<f o0r xa n d i s c o n t i n u o u s .

so it mustr.'anish at tlrepoint.r :0)means that the rveithtinganrplitudeof the
cos(Ax)termmustr,'anish becausecos(Ar): I at-t : 0. That is.
B =0. (1.67)
The amplitudeof the sin(rt,r)rerm is not affecredby the conditionthat {r vanish

ot.r : 0. sincesin(t.r) itselfr.anishes
at,r : 0. So.nou,weknou,that{r is really
of the forn:
/(.r):.{ sin(tr-). (1.6[i)
The conditionthat 1/ralsovanishat -v : I hastrvopossibleimplications. Either

. 4 : 0 o r f r m u s tb e s u c ht h a t s i n ( A l ) : 0 . T h e o p t i o nI : 0 w o u l dl e a dt o
an answerry'that vanishesat all valuesof -r and thusa probabilitythat vanishes
everywhere. This is unacceptable because it rvouidimplv thattheparticleis never
observedanywhere.
The otherpossibilityis that sin(ft1): 0. Let'sexplorethis ansrver becausert
offers the first exanrpleof energyquantizationthat you have probablyencoun-
tered.As you know.the sinefunctionvanishes at integralmultiplesof :r. Hence
AL mustbe somemultipleof :r: let'scall the integern andu'riteZA : rz (using
the definitionof fr) in the form:
Lt}nEllitt): nn. (r.69)
Solving this equation for the energy f , we obtain:
E : n1r2rt
l(2mt). (r . 7 0 )
This result saysthat the only energyvaluesthat are capableof grving a wave
function ry'(x)that will obey the aboveconditionsare thesespecificE r.alues.In
otherwords,not all energyvaiuesare"allowed"in the sensethattheycanproduce
ry'functionsthat are continuousand vanishin regionswhere z(x) is infinite. If
one usesan energyE that is not one ofthe allowedvaluesand substitutesthis E
into sin(*;r),the resultantfunctionwill not r,anishat x : L.I hopethe solutionto
this problemremindsyou of the violin stringthatwe discussedearlier.Recallthat
the violin stringbeing tied down at x : 0 and at -r : z gaverise to quantization
of the wavelengthjust asthe conditionsthat ry'be continuousat;r-: 0 ar.rdx : Z
gaveenergyquantization.
Substitutingk : nn /L into ry': I sin(k,r)gives
VQ)= Asin(nrx/L) (r.7r)

The valueof I can be found by rememberingthat lq/ l2 is supposedto represent
theprobabilitydensityfor finding the particleat x. Suchprobabilitydensitiesare
supposedto be normalized.rneaningthat their integralover all x valuesshould

amountto unity. So, we can find I by requiringthat
f r
t: l l t t r ) l i , / . t: l . -1t : s i n 2 t r xz I L ) t t x . 0.72)
J ;l
where the integral rangesfrom r : 0 to x : L. Looking up the integral of
sin:(a,rI and solving the aboveequationfor the so-callednormalizationconsranr
I gtves
A : (2lDtt2 (1.73)
andso
/(-r) : (2111trt sin(nrx I L) (r . 7 4 )

Thevaluesthatn cantakeon aren : l, 2. 3. . . .; the choiceie : 0 is unaccentable
becauseit would producea wavefunction ry'(.t)that vanishesat all r.
The full ,r- and t-dependentwavefunctionsare then given as
v ( , r . r ) : ( : ) ' r i n ' ' l ' r' . r l - . t ' : : ' ! l (r.75)

\ L / L lttl L-/lt
L )
Noticethatthe spatialprobabilitydensitylv1,r. r)12is not depenclent

on timeand
is equalto lry'(.r)12
becausethe complexexponentialdisappears when v*w is
formed.This meansrhatthe probabilityof findingthe particleat variousvalues
of "r is time-independent.
Anotherthing I wantvou to noticeis that,unlikethe classicaldynamicscase.
notall energyvaluesE areallor.ved. In theNewtoniandynamicssituation,E could
be specifiedandthe particie'smomentumat any-r valuewas thendetermined to
within a sign.In contrast.in quantummechanics onemustdetermine,by solving
the Schrcidinger equation.rvhatthe allowedl'aluesof 6 are. TheseE valuesare
quantizedmeaningthattheyoccuronly for discretevalues.t : ,2 r2h)
/(2r, L2)
determinedbv a quantumnumberrr. by the massof the particlem, andbychar-
acteristics ofthe potential11.in this case).
1 . 3 . 4P r o b a b i l i t yd e n s i t i e s
Let's now look at sorne of the wave functionsv(.r) and compare the proba-
bility densitieslv(.r)ir that they representto the classicalprobabilitydensities
discussedearlier.The n : 1 and n : 2 wave functions are shown in the top
of Fig. 1.8.The corresponding probabilit-v
densitiesare shownbelowthe wave
functionsin two tbrmats (as n--vplots and shadedplots that could relateto the
flashinglight way of monitoringtheparticle's locationthatu'e discussed earlier).
A more completesetof r.vavefunctions(for izrangingfrom 1 to 7) are shownin
F i e .1 . 9 .
zo T h e b a s i c so f o u a n t u mm e c h a n i c s
,ffi'ffi
n:2
The two
lowest wave functions
and probability
densities.
{
V.
m,axffita;,;*r
25 mau,*ffiu,,*;r
Node
t6
9
Seven
lowestwave functions I
andenergies.
I
M o t i o n o f a p a r t i c l ei n o n e d i m e n s i o n
27
Noticethat as the quantumnumbern increases, the energyE also increases

lquadratically rvith n in this case)andthe numberof nodesin v also increases.
Also notice that the probability densitiesare very different from what we en-
countered earlierfor theclassicalcase.Fo[ example.look at ther : I andil : 2
densities and comparethem to the classicaldensityillustratedin Fig. 1.10.The
classical densityis easyto understand becausewe arefamiliarwith classicaldy-
namics.In this case,we saythat P(.r) is constantwithin the box because the fact
that tr/(.r) is constantcauses rhekineticenergyandhencethe speedofthe particle
to remainconstant.In contrast.the r : I quantumu'avelirnction'sp(.r) plot is
peakedin the rniddleof the box and falls to zeroat the walls.The n :2 density
hastwo peaksP(-r) (oneto the leti of the box midpoint.and one to the right).a
C l a s s i cIa
nodeat the box midpoint.and falls to zeroat the walls.one thing that students p r o b a b i l i t yd e n s i t yf o r
"how
oftenaskme is doesthe particlegerfrom beingin the lefi peakto beingin p o t e n t i a l s h o w n .
theright peakif it haszerochanceof everbein_q at the midpointwherethenode
is?"The difficr"rlty rviththis questionis rhatit is posedin a terminologytharasks
for a classicaldynamicsanswer. Thatis.by asking"horvdoestheparticleget. . ."
one is dernandingan answerthat involvesdescribingits motion (i.e..it moves
from hereat time t1 to thereat time 11).Unfortunatell,. quantummechanics does
notdealwith issuessuchasa particle's trajectory(i.e..rvhereit is at varioustinres)
butonly vu'ithits probabiltyof beingsomewhere (i.e.,lw l:;. The nc'xtsectionwill
treatsuchparadoxicalissuesevenfirrther.
1 . 3 . 5C l a s s i c aaln d q u a n t u mp r o b a b i l i t d
yensities
As.lustnoted,it is temptingfor mostbeginningstudentsof quanturnmechanics
to attemptto lnterpretthe qr-rantum behaviorof a particlein classicalterms.
However.this adventureis tull of daneerandboundto fail becar-rse srnall.light
particlessimply do not moveaccordingto Nervton'slarvs.To illustrate.lets try
to "undersrand"r'"'hatkind of (classical)motion wor-rldbe consistenrlvith the
ri : I or n :2 quanturnP(_r)plotsshownin Fig. 1.8.However.as I hope
1,ou
anticipate.thisattcrnptat gainingclassical understanding of a quantumresultrvill
not "work" in that it r'"'illleadto nonsensical results.My point in leadingyou ro
attemptsucha classicalunderstanding is to teachyou thatclassicalandquantum
resultsaresimplydifferentandthatyou mustresisttheurgeto imposea classical
understanding on quantumresults.
For the zr: I case,we note that P(x) is highestat the box midpoint and
vanishesat.r : 0 and,r : L. Lna classicalmechanicsworlcl this would mean
that the particle movesslowly near-y : L/2 andmore quickly near-r : 0 and
r : L. Becausethe particle'stotai energyE must remain constantas it moves.
in regions where it moves slowlv. the potential it experiencesmust be high.
and where it moves quickly, tr/ must be small. This analysis (n.b., basedon
classicalconcepts)would leadus to concludethat the n : I p(i arisesfrom tne
particlemoving in a potentialthat is high near.r : L

/2 anrlloll, as-r:approaches
0orZ.
A similaranalysisof the n :2 P(x) plot would leadus to concludethatthe
particlefor which this is the correctp(_r) rnustexperiencea potentialthat
is
high midwaybetween:r: 0 and x : L/2,high midu,ayberu,een .r : L 12 and
x = L , a n d v e r y l o w n e a r x: L / 2 a n d n e a r - r: 0 a n d r : r . T h e s e c o n c l u s i o n s
are"crazy"becausen'e know that the potentialt,(-r)for which we solvedthe
Schrodin-eer equationro generatebothof thewavefunoions (andbothprobability
densities)is constantbetween-r : 0 andt : L. That is. ."veknow the samel,(-r
)
appliesto theparticlemovingin thell : I andr : 2 states. whereastheclassical
motion analysisofferedabovesuggeststhat l,(l ) is differentfor thesetwo cases.
what is wron-qrvith our attemptto understandthe quantump(.r) prots?
The
mistakewe madewas in attemptingto apprythe equatio'sandconcepts
of clas-
sicaldynarnicsto a P(.i-)protthat did not arisefrom classicarmotion.
Siniply
put' one can not ask how the particleis mo'ing (i.e..what is its
speedat vari-
ouspositions)whentheparticleis undergoing quantumdynamics.Most students.
r,r'hen
first experiencingquantumrvavefunctionsandquantumprobabilities,
trv to
thinkof theparticlemovingin a classicalway thatis consistenl with thequantum
P(-r). This attemptto retaina degreeof classicalunderstanding of theparticle's
movementis alwaysrnetwith frustration,as I illustratedu,ith the above
examole
andwill illustratelaterin othercases.
continuingwith thisfirstexarnpleof hou'onesolvestheSchrodinger equatlon
and how one thinks of the quantizedE 'alues and u,avefunctionsv,
let me
offer a little more optimisticnote than offeredin the precedingdiscussion.
If we
examinethe w(.-v) plot shownin Fig. 1.9fern :7, andthi'k orthe corresponding
P(;r) : lv(x)12,we notethatthe p(.r-)plot rvouldlook somethinglike that
shown
in Fig. 1.11.It would havesevenmaximaseparated by six nodes.If we wereto prot
I
0.9 11 iI h
0.8 I \ 1 I
0.7 r
^. (\A
5
r! 0.5
V o.c I
I
I
0.3
0.2 I I
0.1 I
I
Ouantum
probabilitydensityfor I I
n : 7 s h o w i n gs e v e n
peaksand six nodes.
0 v rJ \
xlL
: 55,we would find a P(,r) plot having

1V (.r) lr for a very larger valuesuchasn
55 maxima separatedby 54 nodes,with the maxima separatedapproximately
" c o a r s eg r a i n e d "
b ) , d i s t a n c eosf ( 1 / 5 5 I ) . S u c ha p l o t ,w h e nv i e w e di n a sense
1i.e.. focusinu with somewhat blurred vision on the positions and heights of
the maxima) looks very much like the classical P(,r)plot in which P(.r) is
constantfor all -r. In fact, it is a general resultof quantummechanicsthat the
quanfumPt.r) distributionsfbr largequantumnumberstake on the form of the
classicalP(-r) for the samepotentialZ that was usedto solvethe Schrodinger
equation.It is also true that classicaland quantum results agree when one is
dealingwith heavyparticles. Forexample,a givenparticle-in-a-box energvCn :
n:h: I \2ntL2) u,ouldbe achievedfor a heavierparticleat highern-valuesthanfor
a lighterpalticle.Hence,heavierparticles,movingwith a givenenergyE. have
higherr and thusmoreclassicalprobabilitydistributions.
\!'e rvill encounter thisso-calledquantum-classical correspondence principle
'nve
again "r,'hen examineother model problems.It is an important property of
solutionsto the Schrodinger equationbecauseit is what allowsus to bridgethe
"gap" betrveen usingthe Schrodinger equationto trearsmall,light particlesand
theNewtonequationsfor macroscopic (big, heavy)systems.
Anotherthing I u'ould like you to be arvareof concerningthe solutionsry'
and .E to this Schrodinger equationis that eachpair of wavc functionsry',,and
r/r,,belongingto difl-erent qltantumnumbersn andn'(and to differentener_qiesl
displaya propert,vterrnedorthonormality. This propertymeansthat not only are
tfr,,and,{r,, eachnormalized
r t
l: ltrlt,,:,/t:/ .a,,:lt'. (1.16)
J , J
but they are also orthogonalto eachother
o= lr',t,,,r',t,,,
a, (1.77)
where the complex conjugate* of the first function appearsonly when the ry'
solutionscontainimaginarycomponents (you haveonly seenone suchcasethus
far - the exp(ill @) eigentunctions
of the:-componentof an-qular
momentum).It
is commonto write the integralsdisplayingthe normalizationand orthogonality
conditionsin the fbllorvineso-calledDiracnotation:
| - / r l r ,|, 1 1 , , \ 0: 1 r l t , ,r' ! , , ) . (1.78)
where the l) and (l si'mbolsrepresenttb and lt*, respectively,and putting the

two togetherin the (l) constructimpliesthe integrationoverthevariablethatry'
dependsupon.
The orthogonality conditioncanbe viewedas similarto the conditionof two
vectorsv1 and v2 beingperpendicular. in which casetheir scalar(sometirnes
called"dot") productvanishes .
Vl vr : 0. I wantyou to keepthispropertyin mind
5U T h e b a s i c so f q u a n t u mm e c h a n i c s
because not only of theseparticle-in-

you r.l'illsoonseethat it is a characteristic
a-box wave functionsbut of all w,ar.,efunctionsobtainedfrom any Schrodinger
equatlon.
In fact, the orthogonalityproperty is evenbroaderthan the abovediscusston
suggests.It turnsout that all quantummechanicaloperatorsforrnedas discussed
earlier(replacingCartesianmomentap by the corresponding -ihd ldq operator
and leat'ingall Cartesiancoordinates as thev are) can be to be so-called
shor'vn
Hermitianoperators. This rneansthat they form Hermitianmatricesu'henthey
are placed betweenpairs of functionsand the coordinatesare integratedover.
For example,the rnatrix representation of an operatorF vu'henacting on a set of
functionsdenoted{dr} is
F rL : ( Q t t F t Q: L t * ; r r ' u , (1 . 7 e )
|
For all of the operatorsformed following the rules statedearlier.one finds that
thesematriceshavethe followingproperty:
rr J _I -r +r / t . r1.80)
rvhichmakesthe matricesu'hat we call Hermitian.lf tlre functionsupon u'hich

F actsand F itseifhaveno imaginaryparts(i.e..arereal).thenthe tnatricesturn
out to be svmmetric:
F r . L: Ft.r ( r . 8 )l
The importanceof the Hermiticity oI symlnetryof thesematriceslies in the fact

tl.ratit canbe shownthat suchmatriceshaveall real(i.e.,not cor.t.rpler)
eigenvalues
and haveeigenvectors that are orthogonal.
So, all quantummechanicaloperators,not just the Hamiltonian,have real
eigenvalues(this is good since theseeigenvaluesare rvhat can be measuredin
any experimentalobservationof that property) and ortho-qonaleigenfunctions.
It is importantto keep thesefacts in mind becausewe make use of them many
times throughoutthis text.
1 . 3 . 6T i m e p r o p a g a t i o no f w a v e f u n c t i o n s
For a systemthat existsin an eigenstateV(x) : (2lL)t12 sn(nitx lL) havingan
energyEn : n2r2h2lQmLz),the time-dependent u'avefunctionis
r): (?)"',inff*r(-?),
v(x. (1.82)
which can be generated by applying the so-called time evolution operator U(l' 0)
to the wave function at I : 0:
V(x.r) : U(r,0)v(,r,0) (1 . 8 3 )
rvherean explicitform for U(t, t') is
L ( r .r ' \ : . * o[ - " ' *'''"-l. (1.8+.)

L n l
Thc-functionV(.r, t) has a spatialprobabilitydensitythat doesnot dependon
timebecause
v.(.r. : (;) ""' (?)
r)v(.r.,, (1 . 8 5 )
sinceexp(-rtE,'l/i) exp(itE,,l/i) : l. However it is possibleto preparesystems

(evenin real laboratorysettings)in statesthat are not singleeigenstates;we call
suchstatessuperposition states.For example,considera particlemovingalong
within the "box" potentialbut in a statewhosewave function at some
the-r--axis
initialtime/:0is
, / l \ l : / 1 7 r \ . . r 2 t l : / l - z . r ' \
u(ror:,,,(;)'''( {r86)
. )-,,(;),'"(?)
T h i s i s a s r - r p e r p o s i t i o n o f t h eIna:n d z : 2 e i g e n s t a t e s . T h e p r o b a b i l i t v d e n s i t y
a s s o c i a t endi t h t h i s f u n c t i o ni s
r,r,r' | (?) - r(?)

: I ;,'",(?) +/ sin:
lrr\
' t ' n /( / 1 . - r .tr I
(1.87)
r /t'"( . ,/i
Then : I andn : 2 components, the superpositionV. andthe probabilityden-
:
sityat 1 0l V lr areshownin thefirstthreepanelsof Fig. l. 12. It shouldbe noted
that the probabilitydensityassociared with this superposition srateis not sym-
metricaboutthe"r : I/2 rnidpointeven thoughthen : I andn : 2 component
wavefunctionsand densities are.Sucha densitydescribes the particlelocalized
more stronglyin the large-"vregionof the box than in the small-,rregion.
Now. let's considerthe superpositionwave function and its densitl,at later
times. Applying the time evolutionoperator exp(-itHl/i) to V(r,0) generates
thistime-evolved tunctionat time /:
",'"
' { i ) ' , , " ( T ) - ' ' '(?r)
v ( ;rr1 *: ' ( - # )
{, (?)l
:
['
' ( ; )" ' ' ( ? ) ' - io) (- -' ' ,'G)"'
"',"(?).-'(-+)] (r.88)
The spatialprobabilitydensityassociatedwith this W is
,)r::
rv(r j{(;),'",(+)
. (;),,'',(?)
-'(?).o, - u,)if,',
(+),'"(?)] o8e)
[ru,
5Z
I
d o.E r I--r\ u.l
0 ^ --
/ i I \
E t,.o
/f 06 !_t
\ f_' t I
l i . . - lt .l 0.i
I
.- 04
(1.-l / l
I
{
^ _0.1
{ ()l t
> {)l
t
t
= = 0 I
\ j
( 1I.
-t ! 7
-0:
X,L
1.6
{ ^l i. { -1^
t: t.l / \ I
\
J
f
1 6l
I
I
0 N i \
.\
0.6
t:
.=
I
I
1).1 I a
: d a
|I,
vi )
L_] -
jflff r h e n : 1 a n d n : 2 w a v e f u n c t i o n st,h e i r
s u p e r p o s i t i o na,n d t h e
a n dt i m e - e v o l v ep
d r o b a b i l i t yd e n s i t i e so f t h e
superposition.
At r : 0' this functionclearlyreducesto that

u,rittenearlierfor v(r.0). Notice
thatastimeevorves. thisdensitychanges because of thecos[(82- E 1ltf til factor
it contains'In particular,note that as r moves
through a period of rength6l :
n h/ ( E 2 - f r ). the cosfactorcha'gessign.
Thatis. for r : 0. the cosfactoris + l
f o r l : r / i / ( E 2 - t r ) , t h ec o sf a c t o r i s_ l ; f o r : 2 r / i l ( E z _ ;
t E r ) . i t r e t u r n st o
* L The resultof this time variationin the cosfactor
is that lV l: .lrun-c.,in forn.r
from that shownin the bottom left paner
of Fig. l .12 to tr-ratshou,n in the bottom
right panel (at t : trril(E2 - 6r)) and then
back to the fbr'i in the bottom reft
panel(at t : 2tr11/(Ez- E
t)). one caninterpretthistime variationasdescribing
the particlekprobabilitydensity(not its
classicar positionl),initiaily Iocalized
toward the right side of the box, moving
to the left and then back to the rr_qht.
of course,this time evolutionwill continue
overmore and more cycresas trnre
evolves.
This exampleiilustratesonce againthe
difficulty with attemptingto locarize
particlestliat arebeingdescribed
by quantumwave-functions. For exampre.a par-
ticle that is characterized by the eigenstate (2/ D) /2 sin(tr x I L) i, rn"rill*.,u ,"
be detectedfleor'i : L/2thannearir :0
orrj - r becausethe squareof this
f u n c t i o n i s l a r g e n e a r=- rL / 2 . A p a r t i c l e i n t h e s t a t e
(2lDt/2rin1:n..7tj,smort
l i k e l i z t ob e f o u n d r €& r x: L / 4
a n dx : 3 L f 4 , b u t n o t n e a r , r: 0 , x : 1 1 t . s y
M o t i o n o f a p a r t i c l ei n o n e d i m e n s i o n J5
.r = L. The issueof horv the particle in the latter statemovesfrom being near
r = L f 4 to x : 3 L l4 is not somethingquantummechanicsdealsrvith.euanfum
mechanicsdoesnot allow us to follow the particle'strajectory.which is what we
needto know whenwe askhow it movesfrom oneplaceto another.Nevertheless.
superposition wavefunctionscan offer"to someextent,the opportunityto tbllow
the motionof the particle.For example,the superpositionstatewritten aboveas
2 - r , : 1 2 1 1 1 1s1i n2( l z - r l Z )- 2 - t / 2 Q l L ) t / 2 s i n ( 2 n x l L ) h a s a p r o b a b i l i t y a m p l i -
tude that changeswith time as shown in the figure. Moreover,this amplitude's
major peakdoesmove from side to side within the box as time evolves.So, in
this case.we ciln say with what frequencythe major peakmovesback and forth.
"follorv"
In a sense.this allor.vsus to the particle'smovements.but only to the
extent that'"ve are satisfied with ascribingits locationto the positionof the major
peakin its probabilitydistribution.That is, we can not really foilor.vits "precise"
location.but we can follor,vthe location of where it is very likely to be found.
This is an importantobservationthat I hopethe studentwill keepfreshin mind. It
is alsoan importantingredientin modernquantumdynamicsin which localized
wavepackets,similarto superposed eigenstates, are usedto detailthe position
andspeedof a particle'smain probabilitydensitypeak.
Thc-aboveexampleillustrateshow one time-evolvesa \ryavefunctiontharcan
be expressed as a linearcombination(i.e..superposition) of eigensrates of the
problem at hand. There is a large amount of current eftbrt in the theoreti-
cal chemistrycommunityaimedat developingelicient approximations to the
exp(-i t H lll) evolutionoperatorthatdo not requireV(.r. 0) to be explicitl_y rvrit-
tenasa sumof eigenstates. This is importantbecause, for mostsystemsof direct
relevanceto molecules,one can not solvefor the eigenstates; it is simply too
difficult to do so. You can find a significantlymore detailedtreatmentof this
subjectat the research-level in my TheoryPageweb siteand my el,tIC tertbook.
However.let'sspenda little time on a brief introductionto what is involved.
The problemis ro expressexp(-itHlh)V(qr), whereV(qr) is some initial
wave function but not an eigenstate,in a manner that does not require one
to first find the eigenstates{V7} of H and to expand V in terms of these
eigenstates:
v:fc,w, ( 1.e0)
J
afterwhich the desiredftlnction is written as
:
"t (-#) v@,)
1,,*,*,(-+) (l.er)
The basicideais to breakH into its kinetic I andpotentialtr/energycomponents

and to realizethat the differentialoperatorsappearin I only. The importance
of this observationlies in the fact that I and Z do not commute,which means
thaLTV is not equal to ZI (n.b.,for two quantitiesto commutemeansthat their
order of appearancedoes not t.natter).Why do they not conrmute'lBecauseI

containssecondderivatives n'ithrespecttothecoordinates {q , } that I' dependson,
so.for example,d2I d q2LI,@)V (q )l is not equalto Il (q ) d2i d (12V (r7). The fact
that r and l' do not commuteis inrportantbecausethe rnostcommon approach
to approxrmating exp(-rlH/fi) is to rvritethis singleexpor.rential in rerms of
exp(-itTlh) and exp(-lri.'/fi). However.the identity
*'(-f):*'(-+)
*'(-f) (l q2)
is not fully valid as one can seeby expanding all threeofthe aboveexponential
f a c t o r sa s e x p ( . r ) : I * . r - + x 2 / 2 ! * . . . . a n d n o r i n _tqh a l t h e r $ , os i d e so f t h c
aboveequationonly a-eree if one canassulnethatTl': I'L u,hich.as rvenoted-
is not true.
In mostr.nodern approaches to time propagation. onedividesthe time interval
r into nrany(i.e..P of them) small time "slices"r : t / p. onc then expresses
the evolutionoperatoras a productof P short-timepropagators:
itH\ rrHl
e x /p ( - , , : . * o /l - - ) . - o ( -I ; , i) t. H- n\ ( - r i r H t
/ ; )
irtl\lr
: I t
(r.e3)
L ' * n \ -t / l
If one can developan efficient rneansof propagatingfor a short time r. one
can then do so over and over again P times to achievethe desiredfull-time
propagation.
It can be shown that the exponentialoperatorinvoll'ing 11 can betterbe ap-
pro.ximated in terms of the f and I/ exponentialoperatorsas follows:
rrH\ . -t f- t-'F- V
/ \-
exp l - ln. *\ p ( -/ irr'\ r irr\
(r.e_r)
ft /-.*pt,-. a /.-o(_;/
So. if one can be satisfiedwith propagatingfor very short tirne ir.rtervals
(so that
the rl term can be neglected),one can indeeduse
*'(-#)-*p(-+)-'(-T) (r.e5)
as an approximationfor the propagatorU(r, 0).

To progressfurther, one then expressesexp(-irT//1) acring on the initial
function v(q) in terms of the eigenfunctionsof the kinetic energy operator
r. Note that these eigenfunctionsdo not dependon the nature of the poten-
tial z, so this stepis valid for any and all potentials.The ei_eenfunctions
of r :
-n-
*1 ,^ rt , , f
/ tntd'/ctq' arc
, ! , , ( q ) : ( * )*' "r ( T ) ( 1.e6)

35
andthey obeythe following orthogonality

f
V i , t a t t l r , , ( q t :d q3 r p - p l (r . 9 7 )
J
relations
andcompleteness
rL,.t,t \lp = |rq - q t.

trlr,",tt1 (r . e 8 )
J
Writing V(q) as
v ( q ) : I A u- ( ] ' ) v ( q ' ) d q , . (1 . e 9 )
for d(q - q') gives

andusingthe aboveexpression
rr(q) : )rtt(q'ytq'ttp.
v,,u,,,t';,,q' (1.100)
| |
Tlreninsertin-etheexplicitexpressions
for tlr,(c1)andr!
r'z ;(q' ) in termsof ,,ft 1:
,,1c1
0 l2ir 1t pr7
exp(i /fi) -erves
. I tr:
Q t ' 7 t :f f l |
' * o1( ;i l7 r 4( 1; ,7) 1 r :. . - o/ ( -i p# u) t Q r 't '1t ' 1 ' t p r r r 0 r t
JI \; J
Now.allor.ving
exp(-i r T lIt)to act on this form for W(r7)produces
. . P/ ( i r T )\ w t q , :r r / ; ' , ' r t i \ /I
\''
n JJ . ' p ( ' # l l r ; t
^ . *' oL[ ? , u : , ,, l f : ) ' ' ' * , r , r o r , r , ( r r 0 2 )
) \ h t h
The integralover p abovecan be carriedout analyticallyanclgives
. * P/(
irT\. 1 m r : / f i n r q _ 4 ' t : \l t t t , t ' ) , t " t
n ) q , , t , : ( : r , r , ) 7 . * oL ," 1
. rr.l03r
So, the final expressiontbr the short-time propagatedwave function is
t f , n t \ ' t f - . ^ f i n t 1 t- 1( t 7 : 1
v"{' ,,r ."r-) ": .u* L
o[-irli'l (.,,r/ {1.10+)
/r-j 7.*pL ,* lVtt1'td,l.
whichis theworkingequationoneusesto computeV (q , t )knowingV (4). Notice
thatall oneneedsto kno."r,
to applythis formulais the potentia1 v (q) ateachpornt
ln space.one doesnot needto know anyof the eigenfunctions of the Hamiltonian
to apply this method.Howe'u'er. one doeshaveto use this formula over and over
agarnto propagatethe initial wavefunction throughmany small time stepsr to
achievefr"rllpropagationfor the desiredtime intervalt : pt.
Becausethistypeoftime propagationtechniqueis a very activeareaofresearch
in thetheorvcommunity.it is likely to continueto berefinedandimproved.Further
discussionof it is beyondthe scopeof this book, so I will not go further in this
direction.
1.4 Freeparticlemotions in more dimensions

T h e n u m b e r o f d i m e n s i o n sd e p e n d so n t h e n u m b e ro f p a r t i c r e sa n d
the
number of spatial {and other) dimensions needed to characterize
the
positionand motion of each particle.
1 . 4 . 1T h e S c h r o d i n g eer q u a t i o n
consideran electronof massri and chargee mo'rng on a tlvo-dimensionar
surfacethatdefinesthex, -r.plane(e.g.,perhapsan electronis constrained to the
surfaceof a solid by a potentiarthat binds it tightly ro a narro\\,regio' in
the
---directio.).and assumethat the electronexperiences a constantand not trrne-
varvrngpotentialI1t at all pointsin this plane.The pertinenttinre-independent
S c h r o d i n g ec rq u a t i o ni s
-t t /a t a t\..
+ 'drt L i t l t ( x " r ' ) :E f ( ' r " r ' ) (1 10-5)
\a"t' )t(r't')*
The task at hand is to solve the aboveeigen'alueequationto deternrine
"allorved" the
energystatesfor this electron.Becausethereareno termsin this equa_
tion thatcouplemotionin the; and l directions(e.g..no ternlsof the
form,t,-r.b
or Sldx 0/Ev or x 0/8v),separation of'u'ariabres
canbe usedrowrite y'rasaprod-
uct U(r. -r'): l(.r)BLr,). Substitution
of thisforrnintotheSchriidingerequarion,
followedby collectingtogetherall r-dependentandall
terms,
_r'-dependent _qrves
rf 1a]A rt ta2a
2*7ar;- (l'106)
2-E *:E-rtt'
Since the first term contains no r,-dependence and the second contains no
x-dependence. and becausethe right sideofthe equationis independentofboth
x and -r,,both terms on the left must actuallybe constant(thesetwo
consranrs
are denoted E" and Er', respectiveiy).This observationailows two
seDarare
Schrcidinger equationsto be written:
rt . alA
- - / - ' - - F -
(1.107)
ztn dx.
and
- i l b^ - , f B = r ) ' ' (l'lo8)

2m ai
The total energyE can then be expressedin termsofthese separate
energiesE,
and E, as E, + E:, : E - 20. Solutionsto the x- and
.quations
,t,-Schrcidinge.
areeasilyseento be:
A(x):*o[,,.
I r '-l
(+)"'] .
ano
| / 2 n E .t ' - |
expl-ilt -.1
\ t r /
| (l.t09t
L l
B(,r'):.*p[,r,
(ry)"] a n d . ^ o [ - (, ,+ ) " 1 ( rr o )
L \ r )
F r e ep a r t i c l em o t i o n si n m o r e d i m e n s i o n s '71
Trio independentsolutionsare obtainedfor eachequationbecausethe,r- and

Schrodinger
.r.-space equationsarebothsecondorderdifferentialequations
(i.e..
a secondorderdifferential
equationhastwo independentsolutions).
1 , 4 . 2B o u n d a r yc o n d i t i o n s
T h e b o u n d a r y c o n d i t i o n s ,n o t t h e S c h r o d i n g e re q u a t i o n ,d e t e r m i n e
w h e t h e rt h e e i g e n v a l u e w
s i l l b e d i s c r e t eo r c o n t i n u o u s .
If theelectronis entirelyunconstrained within the-r. _r'plane,theenergiesE,

and 8.,.can assumeany values:this meansthat the experimenter can "inject"
rhe electrononto the,r.r'plane with any total energyE and any components
8., and ^t.,.alongthe two axesas long as E^ + E;. : E .In sucha situation.one
speaks ofthe energies alongbothcoordinates asbeing"in thecontinuuln"or'.not
quantized".
In contrast. if theelectronis constrained to remainwithin a fixedareain the.r.,r,
plane(e.g.,a rectan-eular or circr.rlar region),thenthe situationis qualitatively dif'-
i'erent.constrainin-e the electronto any suchspecifiedareagivesriseto boundary
conditionsthatimposeadditionalrequirements on the aboveA anJB fLrnctrons.
Theseconstraints can arise,for example,if the potentiall,ii(.r._r,)becornes verv
Iargetbr,r. .i valuesoulsidetheregion,in r,vhich caserheprobabilityof fincjinethe
electronoutsidetheregionis very small.Sucha casemightrepresent. for example.
a situationin rvhichthentolecular structurcofthc solid surfacechanges outsidcthe
enclosed regionin a \\'aythatis hi-uhlyrepulsiveto rheelectron(e.g..asin thecase
of molecularcorralson metalstrrfaces). This casecouldthenrepresent a simple
modelof so-called"corrals"in rvhichtheparticleis constrained to a finiteresion
of space.
Forexarnple. if rnotionis constrained to takeplacelvithina rectaneular regron
d e f i n e db y 0 . - r < l , : 0 < , r . < 1 . , . t h e nt h e c o n t i n u i t yp r o p e r t yt h a ta l l w a v e
tunctionsrnustobev (becauseof their interpretation as probabilitydensities.
whichmustbe continuous) causesI ("r) to vanishat 0 andat r , . Thatis. because
.'1mustr.'anish fbr.r < 0 andmustl'anishfor.v > z.r,andbecause A is continuous.
itmustvanishat,r:0andat.r:2.,.Liker.r,ise.B(rr)mustvanishat0andatZ...
To inrplemc'nttheseconstraintsfor I (.r:). onemustlinearlycombinetheabovetwo
s o l u t i o n s e x p [ i , r ( 2Er,rl l i 2 l t i z l a n d e x p [ - r . r ( 2 n E , y / t 2 l r i z l t o a c h i e v e i i f u n c t i o n
thatvanishes at,r : 0:
r(r1:e1p(rf)'"] -.*o "]

(r.ll )
l', [-,,{i+)
one is allowedto linearlycombinesolutionsof the Schrodinger
equationthat
havethe sameenergy(i.e.,are de,eenerate)
becauseSchrcidinger
equationsare
Jd
li,ear differentiarequations'An
analogousprocessmust be appriedto g(,r,)
achievea functionthatvanishes to
at.r,: 0.
B(r -op (t+!\"'l -.*" .. - / 1 1 :.1

\ t i I l - q \ fr ) L(12,,r,
' Lf,.', ;/ rnr2
Furtherrequirin-e
J
A(.r) andB(rr) to,,,anish. respecti'elrrat.r : Z.\ and _ 2,.
s r i e se q u a t i o ntsh a rc a nb e o b e y e d _r,
o n l y i f , f , a n d E , a s s u n rpea r t i c u l avr a l u e s :
T
. r n 1 , , , / 2 n Et t : f |
) l - e r n J - i(r; ' ) l = '
(l- ,iarE,1i:l
L r ir . , r
and
f , 2ntE ,l
e r jP ir . ( f i, ' ^ [ l - ' r /' ]\1 1 1 6r , r l
n
L " ) I, J ; L- ) ll : , rrr4r
Theseequationsareequivalent(i.e..
usingexp(i.r): cos-r,* i sin_i,)to
.s, '- n
[ , l r1\2( n- t-EF; -l :)l l- r l a i E ,l r : l
L l = . i n l z(' r i / rr'ir5t
J L J:u
Knou,ing t h a rs i ng v a n i s h e a
ste- nn,forz : l. 2.
3 . . . . l a l t h o u g ht h es i n ( z r )
function'u'anishes for n :0, this function'anishes
for all -t or.r,,andis therefore
unacceptabre becauseit represents zeroprobabiritydensityat alr points
one concludesthat the energiesE, in space).
a'd.E, canassumeo'ly'alues that
obey
t 1,,, tr , l/2
z,{1+rI =r,o.
\ / r / (t.ll6)
. 1 2 n E ,\ r ' 2
r'I ' .l - /l :n,r,
\ f (1.t17)
^r , - nlr2rt
zilr Li (l.rl8)
nln2tl
d
t ff nu d k
t, - = uith
T;8. n\ and t l , = 1 . 2 . 3 , . . . ( l . l1 9 )
It is important to stressthat it is
the imposition of boundary conditions,
pressingthe fact that the electron ex-
is spatia'y constrained that gives
quantizedenergies.In the absence ,se to
of spatialconfinement"or wjth confinement
only at;r : 0 or Z, or only at y _
0 or 2.,, quantizedenergieswould
realized. rot be
In this exampre,confinementof
the erectronto a finite interval
the 'r and 'r" coordinatesyields energies along both
that are quantizedalong both axes.
the electronis confined"t:lg:l".oJrdinur. If
1.g., u.t*".n 0 < x < 2..) bur not
along the other (i.e., Blu) is eitherrestrictea
ioi,anist aty - 0 or at .1,: L,.
at neirherpoinl).thenthetoralenergy or
E liesin th,
isquantizld
u,i r, i, ""t.Anarogs
orsuch
iinear triatomic morecurehus
;:Tl'.::T;:li.*r;:,TiffT
mo.i than enouj energy in one
of its bonds to
F r e ep a r t i c l em o t i o n si n m o r e d i m e n s i o n s ?a
ruprureit but not much ener,{yin the other bond; the first bond,sener-evlies in
the continuum.br"rtthe secondbond'senergyis quantized.
Perhaps moreinteresting is thecasein whichthebondwith the higherdissoci_
ationenergv is ercitedto a levelthatis not enoughto breakit but that is in excess
ofthe dissociationenergyofthe weakerbond.In this case.onehastw.odegenerate
states:(i) the stron-sbond havinghi-ehinternalener-qy and the weak bondhaving
low energy(/r). and (ii) the stron_e bondhavinglittle energyandthe weakbond
ha'ing more thanenoughenergyto ruptureit (tL). Althou_eh an experimenrmay
preparethe moleculein a statethat containsonly the former component(1.e.,
rlt : Crltr -f C1r2.with cr - l. c: : 0), coupringbetrveenthe two degenerate
functions(inducedby terms in the HamiltonianH that havebeen ignoredin
definingry'1and ry'2)usuallycausesthe true wave function W : exp(_il Hih){.,
to acquirea componentof the secondfunctionastime evolves.In sucha case,one
speaks of internalvibrationalenergyrelaxation(IVR) givingriseto unimolecular
decomposition of the nrolecule.
1 . 4 . 3E n e r g i e sa n d w a v e f u n c t i o n sf o r b o u n d s t a t e s
For discreteenergy revers,the energiesare specifiedfunctionsthat de-
pend on quantum numbers, one for each degree of freedom
that is
quantized.
Returningto thesituarioni'which motionis constrained alongbothares.the

resultanttotal energiesand wavefunctions(obtainedby insertingthe quantum
ener_cy
levelsinto the expressionsfor '1(,r-)g( r.)) are as follor,",s:
- ,l:iT- tT
'
2nLi ( r . 12 0 )
n:n-lr
t r' -_ :
L
tnt Ll.
- . ( r .r 2 l )
E:E,+8,+tr/o. 1.t22)
y ' (r ,: ( + ) ( # ) ' L * o ( " F- .)* o ( # ) ]

1 | \ : / I \ T , : , ,
.[.-o(
+)-.-,(-i:)]
w i t h n , a n di l , = ! . 2 , 3 , . . . (L.l:l)
The two (1/2Dt/2 factorsare incrudedto guaranteethat ry'is normalized:
w o . 1 , ) l 2 dt txv : I ( L 12,{)
t
NormalizationallowsltL(x , y)r2to be properlyidentifiedasa probabiliry
density
for findingthe electronat a point-lr.r,.
40 T h e b a s i c so f q u a n t u m m e c h a n i c s
rffi)
wl
Plots of the
( a )( 1 , 1 )(,b )( 2 , 1 )(,c )
{ 1 , 2a) n d \ d l Q , 2 lw a v e
f u n c t i on s .
Shou'nin Fig. l.l3 are plots of four suchtwo-dimensional u,avefunctions

f o r r r . a n d n , v a l u e so f ( 1 , 1 ) ,( 2 , 1 ) ,( 1 . 2 )a n d ( 2 . 2 ) .r e s p e c t i ' c l .Nv o
. r e t h a tt h e
functionsvanishon the boundariesof the box, and noticehou,tlre nurnberof
nodes(i.e..zeroesencountered as the r.r,ave functionoscillatesfi-ompositiveto
ne-qati\:e) is relatedto the r- and n.,.quantun nurnbersand to the energy.This
patternof more nodessignifying higher ener_rly is one that u,e encounteragain
and againin quantummechanicsand is somethingthe studentshouldbe able
to useto "guess"the relativeenergiesof war.efur.rctions when their plots are at
hand.Finally,you shouldalso noticethat.as in the one-dimensional box case.
an)'attempt to classicallyinterprettheprobabilities p(-r. corresponding to the
-r,)
abovequanturn\4'avefunctionswill resultin failure.As in the one-dinrensionai
case.theclassicalP(.:r'. 1,)wouldbe constant alongslicesof fixed.r-andvaryinu_i,
orslicesoffired,r'andvarying-r r.r,ithintheboxbecausethespeedisconstantther
Hou'ever,the quar.rtum P(x, t,) plots,at leastfor small quantumnumbers,arenot
constant. For larger, andn ,.values,thequantump(r,
l,) plotswill again,via the
quanturn-classical correspondence principle.approachthe (constant)classical
P(.r.,i,)form.
F r e ep a r t i c l em o t i o n si n m o r e d i m e n s i o n s
41
1 . 4 . 4Q u a n t i z e d
a c t i o nc a n a l s o b e u s e dt o d e r i v e
e n e r g yl e v e l s
Thereis anotherapproachthat canbe usedto find energylevelsand is especially
straightforwardto use for systemswhose Schrodingerequationsare separable.
Theso-called classicalaction(denoteds) of a particremovingwith momentump
alonga pathleadingfrom initial coordinateq1at initial time ri to a final coordinate
q r . a rt i m er ; i s d e f i n e db y
s= (r.125)
/*"'R.o{.
Here.the momentufirvectorp containsthe momentaalong all coordinatesof the
system.and the coordinatevector q likewisecontainsthe coordinatesalong all
suchdegreesof freedom.For example,in thetwo-dimensional particle-in-a-box
problemconsidered above,q : ("r..ir)hastwo components
as doesp : (p,.p,,),
and the action integralis
(r.r26)
In computin-u suchactions,it is essential
to keepin mindthesignof themomentum
as the particlemovesfrom its initial to its final positions.An examplewill help
clarify'thesematters.
Forsystemssuchastheaboveparticle-in-a-box examplefor whichtheHamil-
tonianis separable,the actionintegraldecomposes into a sum ofsuch integrals.
one fbr eachdegreeof freedom.In this trvo-dimensional example,the additivity
of H.
H : t i ,- H ,: + - + + v t y t 1v l v t
2n 2n
ti ;;t: - r fi a2
tttt
;:
tt.Y-
I'{.t)- :-:-; * l'( r'). (r.127)
llll dl'-
meansthat p. and p.r.canbe independently solvedfor in termsof the potentials

v(r) and I,'(,u)as well as the energies6. and 6,, associatedwith eachseparate
degreeof freedom:
p, : +r/2i(.1rlo)), (r . r 2 8 )
, / =t t-t l b - , - Y l . v l l ;
Pt= (1.129)
the signs on p, and pr, must be chosento properly reflectthe motion that the
particleis actuallyundergoing.Substitutingtheseexpressions into the action
rntegralyields
s:s,+,s, (1.13())
fi:rf
f f.tfxt
: t f2n1E,- v(t))rr * t vtrt))t/.v.(r.l-ll)
J,,,,, Jr,,,, Jrm@,-
The relationshipbetweentheseclassicalactionintegralsand the existenceol

quantizedenergylevelshasbeenshownto involveequatingthe classicalaction
for rnotionon a closedpathto an integralmultipleof planck'scorlstant:
s . r n .=
" d f q t = c ' p: .t dt q: r i l r ( , : l . ] . 3 . : 1. . . ) . (1.132)
Appliedto eachof the independentcoordinates

of the trvo-dirnensional
particle-
in-a-boxproblem,this expression
reads
r -'r
l,=L
n . , l t= | , 2 t n ( E , - I ' ( , r ) )d t + | - !f/x(l' Jr(.rD./r. (l ljj)
J.-o - l, = r.
f,=t r f,t
n,h: I t t 2 m ( E -, 1 " ( . r . t) l)r + | * r , 1 i 1 E _ t 1 r y ,1l r . il.13.1)
Jr:0 "lt:t,
Notice that the signs of the niomentaare positivein each of the first inre-
g r a l sa p p e a r i n ag b o v e( b e c a u s teh e p a r t i c l ei s m o ' i n g f i . o m . r : ( ) t o . r - : 1 , .
a n d a n a l o s o u s lfyo r . t - l t t o t i o na. n d t h u sh a sp o s i r i r en r o n t c n t u l lrrn d n e l a r i r t
i n e a c ho f t h e s e c o n di n r e g r a l s( b e c a u steh e r n o t i o ni s f r o m . r : l , t o - i - : 0
(andanalogously for.r'-motion)and thusthe particlehasnegativenromentum).
W i t h i nt h e r e g i o nb o u n d e db y 0 . - r -< l . : 0 < , r . < 2 , . t h c p o t e n t l avl a n i s h e s "
so i/(x) : l'lr') : 0. Using this fact. and re'ersingthe upperanti lou,erlinrits.
andthusthe si-sn.in the secondintegralsabove.one obtains
n,h:2 [ ' = t ' , ' 7 , , , qd r : 2 r 5 u , P 1 , . (l.li5)
'='
n, h : 2 1Zn t, tlt. : 2{r,, tr, L, (1.3
16)
[
Solving for E, and 8,. one finds
- (n,h12
(r.r37)
6ri l-;
- (n'h\2
(1.138)
s nL l
Theseare the sarnequantizedenergylevelsthat arosewhen the u,avefunctron
boundaryconditionswerematchedatx : 0. r : 2., and,l : 0..1,: 1,,. In this
case!one saysthat the Bohr*sommerfeldquantizationcondition.
nh : p.de, (1.r3e)
lo't=o""
hasbeenusedto obtainthe result.
Theuseof actionquantizationasillustratedabovehasbecomea very important
tool. It has allowed scientiststo make great progresstoward bridging the gap
betweenclassicalandquantumdescriptionsof moleculardynamics.In particular,
F r e ep a r t i c l em o t i o n si n m o r e d i m e n s i o n s 43
by usingclassicalconceptssuchastrajectoriesandthenappending quantalaction
conditions.people have been able to developso-called
semi-classicalmodelsof
moleculardynarnics. In suchmodels,oneis ableto retaina greatdealof classical
understandingwhiie building in quantumeffects such as energy quantization.
zero-pointenergies.and interf'erences.
1 . 4 . 5O u a n t i z e da c t i o nd o e s n o t a l w a y sw o r k
Unfortunately.the approachof quantizingthe action does not alwaysyield the
correcterpressionfor the quantizedenergies.For example.when appliedto
the so-calledharmonicoscillatorproblemthat we will study in quantumform
later.which servesas the simplestreasonablemodelfbr vibrationof a diatomic
moleculeAB. one expresses the totalenergyas
e:{+\,' (l.l.ro)
tlt t
w h e r e 4 : m ^ n t B l 0 nA f r r s ) i s t h e r e d u c e d m a s s o f tAhBe d i a t o m . firs t h ef o r c e
constant describing thebondbetweenA andB. r is thebond-length displacement.
andp is themomentumalongthebondlen-eth. The quantizedactionrequirement
thenreads
, h: I pd :, I l ' , ( ' -1 , ' ) ] ' ' , , (l.l.1l)
i sl c a r r i e do u tb e t w e e ny = - ( 2 8 l k ) l ' l a n dC E l k l ' 1 . t h el e f ta n d
T h i si n t e - u r a
rightturningpointsof theoscillatorymotion.andbackagainto form a closedpath.
Carryingout this integraland equatingitto nh givesthe followin_q expression
for thc energyE:
, , . 1 2
I I I K \
6-:,,. l-l (1.142)
::r \lL/
rvherethe qLlantumnunrberri is allorvedto assumeintegervaluesrangingfrom

n : 0. l. 2. to infinitv.The problemrviththisresultis thatit is wrong! As experi-
mentaldataclearlyshor'",. thelowestenergylevelsfor thevibrationsof a rnolecule
do not haveE :0: thevhavea "zero-point"energythat is approrimatelyequal
Lo I l2( h l21 11.1;
I p\ti: . So.althoughthe actionquantization conditionyieldsen-
ergieswhosespacings arereasonablvin agreementrvith laboratorydatatbl lorv-
energystates(e.g..suchstateshaveapproxirnately constantspacings), it fails to
predictthe zero-pointenergycontentof suchvibrations.As we will seelirter,a
properquantumrrechanicaltreatmentof the harmonicoscillatoryieldsenc'rgies
of the ibrm
"
E : (,,.:) (*)(:) (1.143)
which differs from the oction-bascdresult by the proper zero-point energy.

Evenu'ith suchdifficultiesknou'n.nruchprogress hasbeenmadein extending

themostelementary action-based methodsto moreandmoresvstemsby introduc_
ing. for exanrple.rulesthat alloll the quantumnumbern to assumehalf-integer
a s ' " v e lal s i n t e - q e r v a l u eCsl .e a r l 1i,1. ' nu ' e r ea l l o w e dt o e q u a ll / 2 . 3 / 2 . 5 1 2 . . . . ,
the earlieractionintegralwouldhaveproducedthe correctresult.However.hou,
doesone know when to allorvr?to assumeonly integeror only harf-integer
or
both integerand half-integervalues?The ansr.vers to this questionare beyondthe
scopeofthis text and constitutean activeareaofresearch.For no$,.it is enough
for the studentto be awarethat one can often find energylevelsby,using
action
integrals. but onerrrustbe carefulin doingso because solnetlmes theanswersare
wrong.
Beforeleavingthis section.it is worth noting that the appearance of half-
rntegerquantumnumbersdoesnot onlv occurin theharmonicoscillator -lb
case.
illustrate.let us considerthe r_- angularmomentumoperatordiscussed
earlier.
As we showed this operator.when con.rputed as the ---componentof r x p, can
b e w r i t t e ni n p o l a r( r . 0 . 6 ) c o o r d i n a t eass
L_ : -ihd /d0. (l.l4l)

The eigenfunctions ofthis operatorha'e the forrr exp(ia@).andthe eigenvalues
arenfi. Becausegeometries with azimuthalanglesequal1o@or equalto * 2r
Q
areexactl)'the samegeometries, thefu'ction exp(ia(t)shouldbe exactlythesame
as exp(ia(Q't hr 1).This can onrybe the caseif a is an integer.Thus.
one con-
cludesthatonlyintegralmultiplesoffi canbe'.allowed"valuesofthe:-cornponent
of angularmomenturn. Experimentalry,,
onemeasures the:-componentof an an-
-eularmomentum bi, placingthe systempossessing the a'gular momentumin a
magneticfield of strengthB and obser'ing how many---corxponent energystates
arise.Forexample,a boronatomwith its2p orbitalhasoneunit of orbital
angular
momentum.so one finds three separate;-co,lponent 'alues r.l,hichare
usually
denotednt : -7, m :0, andnt = L Anotherexampleis offeredby the
scan_
dium atom rvith one unpairedelectronin a d orbital: this atom,sstatessplit
into
five (rr = -2, -1. 0. 1, 2) z--component states.In eachcase.one finds ZL + l
valuesof the r/r quantumnumber,and,becauser is a' integer.2L
+ l is an odd
integer.Both of theseobservationsare consistentwith the expectation
that onlv
integervaluescan occur for Z, eigenvalues.
However.it hasbeenobservedthat somespeciesdo not possess3 or
5 or 7 or
9:-component statesbut an evennumberofsuch states.In particular.
whenelec-
trons,protons,or neutronsaresubjectedto the kind of magneticfield
experiment
mentionedabo'e, theseparticlesare observedto have only two
z-componenr
eigenvalues. Because,as we discusslater in this text. all an-qularmomentahave
.?-componenteigenvaluesthat are separatedfrom one another by
unit muiti_
ples of fi. one is forced to concludethat thesethreefundamentalbuilding-block
particleshave:-componenteigenvalues of u2ri and.-r /2h. The appearance of
F r e ep a r t i c l em o t i o n si n m o r e d i m e n s i o n s 45
half-integer angularmomentais not consistent with the observation madeearlier

that @and Q + 2;r correspondto exactlythe samephysicalpoint in coordinate
space, u'hich,in turn,impliesthatonly full-integerangularmomentaarepossible.
The resolutionof the aboveparadox(i.e., horv can half-integerangularmo-
mentaexist?)involvedrealizingthat someangularmomentacorrespondnot to
the r x p angularmomentaof a physicalmassrotating.but. insteadareintrinsic
propertiesof certainparticles.That is, the intrinsicangularmomentaof elec-
trons,protons,and neutronscan not be viewed as arising from rotationof some
massthat comprisestheseparticles.Insteadsuch intrinsic angularmomentaare
"built in"
fundamental characteristicsof theseparticles.For example.the trvo
I l2l1 and-112h angularmomentumstatesof an electron,usuallydenotedo and
p. respectively. are two internal statesofthe electronthat are degeneratein the
absenceof a magneticfield but which representfwo distinct statesof the elec-
tron. Analogousl,v, a proton has I l2h and -l l2li states,as do neutrons.All such
half-integerangularmomentumstatescan not be accountedfor using classical
mechanicsbut are knorvnto arisein quantummechanics.
Chapte2
r
Model problemsthat form important
starting points
T h e m o d e lp r o b l e m sd i s c u s s e di n t h i sc h a p t e fr o r m t h e b a s i sf o r c h e m i s t s '
understanding o f t h e e l e c t r o n i cs t a t e so f a t o m s ,m o l e c u l e sc, l u s t e r sa, n o
s o l i d sa s w e l l a s t h e r o t a t i o n aal n d v i b r a t i o n am
l o t i o n so f m o l e c u l e s .
2.1 Freeelectronmodel of polyenes

T h e p a r t i c l e - i n - a - b opxr o b l e m p r o v i d e sa n i m p o r t a n tm o d e l f o r s e v e r a r
relevantchemical situations.
The "particle-in-a-box" modelfor motionin tri'odimensions discussed earlier

can obviouslybe extendedto three dimensionsor to one. For two and three
dilnensions. it providesa crudebut usefulpicturefor electronicstateson surfaces
or in metalliccr1'stals,respectivelv.I sayn.retallic
crystalsbecauseit is in such
systems thattheoutemostvalenceelectrons arereasonably rvelltreatedasrnoyilg
freely.Freemotionu'ithina spherical volumegivesriseto eigenfuncrions thatare
usedin nuclearphysicsto describethemotionsof neutronsandprotonsin nuclei.
In the so-calledshellrrodel ofnuclei, the neutronsand protonsfill separates.
p. d, etc. orbitalswith eachtirpeof nucleonforcedto obey the pauli principle
(i.e.,to haveno more than two nucleonsin eachorbital becauseprotonsand
neutronsare fennions).To remindyou, I displayin Fig.2.l the angularshapes
that characterizes. p" and d orbitals.
This samesphericalbox model has also beenusedto describethe orbitals
of valenceelectronsin clustersof rnetalatomssuchas Cs,,,Cu,,.Na,, and their
positiveand negativeions.Becauseof the metallicnatureof thesespecies. their
r"alenceelectronsare essentiallyfree to roam overthe entiresphericalvolurneof
the cluster.which rendersthis simplernodelrathereffective.In this rnodel.one
thinksof eachelectronbeingfreeto roamu,ithina sphereof radiusR (i.e.,having
a potential that is uniform rvithin the sphereand infinite outsiclethe sphere).
Finally.as noted above,this samesphericalbox model forms rhe basisof the
so-calledshell model of nuclearstructure.In this model.one assumesthat the
protonsand neutronsthat makeup a nucleus,both of u,hichare fermions.occuDv
46
F r e ee l e c t r o nm o d e l o f p o l y e n e s
_ k - -m l -,,_.-
-k;3-
-n,,,.,J--=]#1'
@
#
W d olLritli
shapes of s, p, and d
f un c t i o n s .
T h ea n g u l a r
sphericrl-boxorbitals(one set of orbitalsfbr proto's.

anothersr"-t for nc.urrons
because thevare distinguishabrc rro' one another).By pracingthe protonsand
neutronsinto thesc- orbitais.t\\,oto an orbital,one achic.n,es a descriptionof the
energyle'els of the nucleus.Excitedstatesareacliie'ed
by prornotinga neutron
or proton fiorn an clccupiedorbital to a lirtuar (i.e.. pre'iously
unoccLrpied)
o r b i t a i .l n s u c ha r n o d c re. s p e c i a i l sv t a b r en u c l e i
a r e a c h i e ' e dw h e n . . c r o s e d _
s h e l l "c o n l i g u r a t i o nssu c ha s l s : o r l s : 2 s r 2 p 6a r c .
r c a l i z e d( e . g . .a H e h a sb o t h
neutronsandprotonsin Isr configurations).
Theorbitalsthatsol'e theSchroclinger equationi'side sucha spherical boxare
notthesamein rheirraclial"shapes"asthes.p, d. etc.
orbitalsof atomsbecause. rn
atoms.thereis an additionalradialpotentialv(r): -Ze2
lr presenr. Honever,
theirang'larshapes arethesameasin atomicstructure because. in bothcases. the
potentialis independent of d andry'.As theorbitalprotsshou,naboveindicate.the
angularshapesofs. p. andd orbitalsdisplayvaryingnumbers
ofnodal surthces.
Thes orbitalshavenone.p orbitalshaveone.a'd d orbitals
havetwo.Analogous ro
how the numberof nodesrelatedto the total energy
of the particleconstrained
to the ,r, -uplane,the nurnberof noclesin the angular
wave functionsindicates
the amountof angularor rotationalenergy.Orbitals
of s shapehaveno angular
energy,thoseofp shapehavelessthendo rl orbitals.
etc.
48 M o d e lp r o b l e m st h a t f o r m i m p o r t a n ts t a r t i n gp o i n t s
The :z
a t o m i co r b i t a l so f a
c o n . j u g a t ecdh a i no f n i n e
c a r b o na t o m s .
one-dinrensional freeparticlemotionprovidesa qualitatircll,correcrpicturc

fbr :r-electronmotion along tlie p" orbitalsof delocalizedpolvenes.The one
Cartesian dir.nension thencorresponds to rnotionalongthe delocalized chain.In
such a rnodel.the box length z is relatedto the carbon-carbonboncllength
R and the number N of carboncentersin'olved in the delocalizednetrvork
I : (A - l)R. In Fig. 2.2, sucha conjugatednetu'orkinvolvingnine centers
is depicted.In this exan.rple.the box lcngthrvouldbe eighttin.resthe c-C bond
length.The ei-eenstates ry',,(l)andtheirenergies8,, represent
orbitalsinto u,hich
electrons areplaced.in the examplecase.ifnine z electrons arc present(e.g..as
in the 1.3.5.7-nonatetraene radical),the groundelectronicstatewould be reprc-
sentedby a total vnavefunctionconsistingof a productin lltich the lorvestfour
ry'sare doubly occupiedand the fifth ry'is singly occupied:
tU: rlpt[y pltzar[lptJt3atltsBt.aullct']1tr:a. (l.l )
The ---component angularmomentumstatesof the electronsare labeledq andt')

as discussed earlier.
A productlr,avefunctionis appropriatebecausethetotal Harniltonianinvolves
the kineticplus potentialenergiesofnine electrons. To the extentthat this total
ener-gycan be representedas the sum of nine separateenergies,one for each
electron,the Hamiltonianalloll'sa separationof r,'ariables
H=LHU) e.2)
in which eachH(j) describesthe kinetic and potentialenergyof an individual

electron.Recall that when a partial differentialequationhas no operatorsthat
couple its different independentvariables(i.e., when it is separable).one can
use separationof variablesmethodsto deconposeits solutionsinto products.
Tlrus,the (approximate)additivity ofllimplies that solutionsof HtU : EV are
productsof solutionsto
H ( . i ) l / ( rj ) : E i t t i ) . (2.3)
The two lowestn-excited stateswould correspondto statesof the form
tlt^ = ltptlrlplrzqrht')r\grlrplraug5plt5u, (.2.4)
and V'* = tltlutlrlpllrglr:frltza*tlltqctt!+fllttu, (2.5)

F r e ee l e c t r o nm o d e l o f p o r y e n e s
49
wherethe spin-orbitals(orbitalsmultipliedby a or B) appearingin the above

productsdependon the coordinatesofthe variouselectrons.For example,
Irstlrt frtlzatlrzfrlr:ctrL:f lr+ulrsfrlrsa (2.6)

denotes
I'p(r t)l' | fl((2')l/2a(r3)l/zp,' t)rt4qG)1h

fl(r)tltaa(r1)!t5B(rs)ry'5a(re
). (2.j)
The electronic excitation energies from the ground state to each of the
above
excited stateswithin this model would be
. r; T<2
) ,t I J 421
I
2 n tl L 2 Lt I
t : f a": <:"1
and AE'':n:--l -'I ( 2 . 8)
2n lL: Lt J
It turnsout thatthis simplemoderof z-electronenergies providesa quaritatively
correctpictureof suchexcitationenergies. Its simplicityallowsone,for example.
to easilysu-sgest how a molecule'scolor (as reflectedin the complemenrary
color of the light the moleculeabsorbs)variesas the conjugationlengthr.
of
the moleculevaries.That is, longerconjugatedmoleculeshave lower-ener_ey
orbitalsbecauser: appearsin the denominatorof the energyexpression.
As a
result,longerconjugatedmoleculesabsorblight of lowerenergythando
shorter
molecules.
This simpleparticle-in-a-box modeldoesnot yield orbitalenergiesthatrelate
t o i o n i z a t i oenn e r s . i eLsr n l e 'rshsep o r u ' n t i "ai ln s i d et h eb o x " i s s p e c i f i e d .
choosin_s
thevalueof thispotentialll suchrhat ,i) +
lir2ll2 12n1152 /Clis equalto mrnus
thelow'est ionizationenergyof the 1,3,-5,7-nonatetraene radical,givesenergy1e.,,_
els(asE : I/o* lt2h2 l2ntl[n:7tr1; whictrcanthenbe usedasapproximations
t o i o n i z a t i t lenn e r S i e s .
The individual;r-molecularorbitals
JtJ
r = (i)'",in(f ) ( t . e' ), , G [ 3
are depictedin Fig. 2.3 for a model of the 1.3.5-hexatriene
for u'hich "bor
z-orbital sysrem OtJ
the length"I is fivetimesthe distanceR6. bet,"veen neighboring
parrsof carbonatorns.Themagnitude of theAthc-atom centeredatomicorbitalin
the nth:r-molecularorbitalis
-eivenby (2lL)1/2 sin(nrkRlc/ I). In this figure,
positiveamplirudeis denotedby the clear spheres.and
negativeamplitudeis
shownby the darkcnedspheres.where two spheresof rike shading
n='GSgEgD
overrap,the
wave tunction has enhancedamplitude:lvheretwo spheresof different (2iL)t 2 sin\nt.rL); Z :,i x Rc.c
shading
overlap.a nodeoccurs.once again.we notethatthenumberofnodes
increases as Thephases
one rangesfiom the lowestenergyorbitalto higherenergyorbitals.
The readeris of the six molecular
onceagainencouraged to keepin mind this ubiquitouscharacteristic
of quanrum orbitalsof a chain
mechanicalu,avefunctions. containingsix atoms
50 M o d e l p r o b l e m st h a t f o r m i m p o r t a n ts t a r t i n gp o i n t s
{
e
Notle
The nodal
patternfor a chain
c o n t a i n i n gs e v e na t o m s .
This simplemodelallor.l,s
oneto estimatespindensitiesat eachcarboncenrer
andprovidesinsightinto which centersshouldbe rrost amenable to electrophilic
or nucleophilicattack.For example,radicalattackat the cs carbonof thc nrne_
atom nonatetraene systemdescribedearlierwould be more lacile for the ground
statev thanlor eitherv* or w'*. In the former.the unpairedspindensityresides
in ry'5.u'hichhasnon-zeroamplitudeat the Cs site,r-: L
12.ln V* and V,*, the
unpaireddensityis in y'raandr,lr6.
respectively.
both of which ha'e zerodensityat
C5.Tlresedensitiesreffectthe values(2/L)1"2si'(rzARcq/Z of theamplitudes
)
for thiscasein which L : 8 x Rcc for, : 5, 4. and 6, respectivell,. plotsof the
wavefunctionsfor n rangingfrom l to 7 are shor,,,n in anotherforrnatin Fig. 2.4
vyherethe nodal pattern is enrphasized.I hope that by now the studentrs not
temptedto askhow theelectron"gets" from oneregionofhigh amplitude,throu-eh
a node,to anotherhigh-amplituderegion.Remernbersuchquestionsare casr
in
classicalNewtonianlanguageand arenot appropriatewhen addressingthe u,ave-
like propertiesof quantummechanics.
2.2 Bandsof orbitalsin solids

Not only doestheparticle-in-a-boxmodeloffer a usefulconceptualrepresentatlon
of electronsrnoving in polyenes,but it arsois the zeroth-order
model of band
structuresin solids.Let usconsidera simpleone-dimensional.,crystal"
consisting
B a n d so f o r b i t a l si n s o l i d s
\ .l
r
'-q*C7
â
' b ' t ' 6 ' h ' b ' ' } : t " s } } " b ' \ \ Theenergy
l e v e l sa r i s i n gf r o m 1 , 2 ,
S,-$S-*i*$l,-gE*'ed*r*Si-*Sil;'@ r-*lsi*-*qe$,- 3, 4,and an infinite
n u m b e ro f o r b i t a l s .
of a largenumberof atontsor ntolecules, eachr,r,itha singleorbital(the spheres

shorvn)thatit contlibutesto thebonding.Let us arran-ue thesebuildin_r: blocksin
a regular"lattrce"assho','"n in Fig.2.5.ln thetop fbur rorvsof thisfigurewe show
thecasew'ithl. 2. 3. and-l bLrilding blocks.To the lefi of eachro\v.wc displavthe
ener-s)- splittingpatterninto which the buildingblocks'orbitalsevolr,eas rhey
overlapandfbrrndelocalized rnolecularorbitais.Not surprisingly. for r : 2, one
findsa bondingandan antibondingorbital.Forn : 3. one hasoneboncring. one
non-bondin-9. andoneantibonding orbital.Finally.in the bottomro\\i.wc attempt
to show "vhathappensfor an infinitelylong chain.The kev point is that the
discretenumberof molecularorbitalsappearingin the l,.l orbitalcasesevolves
rntoa continuumof orbitalscalleda band.This bandof orbitalenergiesranses
from its bottorn(rvhoseorbitalconsistsof a fullll in-phasebondin-e combination
of the buildingblock orbitals)to its top (r.vhose orbital is a fully out-of-phase
antibondingcornbination). In Fig.2.6rveillustratethesefuily bondingandfully
antibondingbandorbitalsfbr two cases- the bottominvolvings-typebuilding
blockorbitals.andtliu'topinvolvingp-typeorbitals.Noticethatwhentheenergy
gap betweenthe buildingblock s and p orbitalsis largerthan is rhe dispersron
(spread)in energyrvithinthe bandofs or bandofp orbitals,a bandgap occurs
betweenthe hishestrnemberof the s bandand the lowestmemberof the n band.
The splittingbetr,veen the s and p orbitalsis a propertvof the individualatoms
comprisingthe solid and variesamongthe elementsof the periodictable.The
dispersionin energiesthat a given bandof orbitalsis split into as theseatoniic
3l M o d e l p r o b l e m st h a t f o r m i m p o r t a n ts t a r t i n gp o i n t s
Fullranlibonding
f Io^-''-
I Sand [aD '
l-trllrh"lrdirr'
t@*,w,*.,@".
I in .ntii F r r l l rr r n r i h o l r d r r r r :
I
lge ffi ffi ffi ffi

6
s band
@
Thebonding
t h r o u g ha n t i b o n d i n g
e n e r g i e sa n d b a n d
o r b i t a l sa r i s i n gf r o m s
andfrom p orbitals.
F u l J vb o n d i n g
orbitalscombineto form a band is determinedby hou,srronglvthe orbitalson

neighboringatomsoverlap.Small overlapproducessmall dispersion. and larse
overlapyieldsa broadband.
Depending on horvmany'alenceelectrons eachbuirdingblockcontributes, the
variousbandsformedby overiappingthebuildingblock orbitalsof theciinstrtuent
atomswill be filledto variouslevels.Forerample,if eachorbitalshou,nabovehas
a singlevalenceelectronin an s orbital(e.g..as in the caseof the alkalimetals).
the s-bandu'ill be half filled in the ground stateu,ith u and paired electrons.
B
Suchsystemsproducevery -{oodcondumorsbecausetheir partially filled bands
allor.l'electronsto move with very little (e.g.. only thermal) excitationamong
other orbitals in this sameband. on the other hand,for alkaline earth sysrems
rvithtwo s electrons per atom,the s bandwill be conrpletely filled.in suchcases.
conductionrequiresexcitationto thelowestmembersofthe nearbyp-orbitalband.
Finally,if eachbuildingblock werean Al (3s23pry atom,the s bandwtruldbe
full andthe p bandwould be half-filled.Sysremswhosehighesterlergyoccupied
band is completelyfilled and for which the gap in energyto the lor.r'est unfilled
bandis largearecalledinsulatorsbecause theyha'e no way to easily(i.e..with
Iittle energyrequirement)promote some of their higher energv electronsfrom
orbitai to orbital and thus effect conduction.lf the band gap betrveena filled
bandand an unfilled bandis small,it n.raybe possibrefor therr.nalexcitation(i.e..
collisionsrvithneighboringatomsor molecules) to causeexcitationof electrons
D e n s i t i e so f s t a t e si n o n e ,t w o , a n d t h r e ed i m e n s i o n s
53
The valence
a n d c o n d u c t i o nb a n d s
and the band gap.
from the formerto the lattertherebvinducingconductivebehavior.An erample

of sucha caseis illustrared
in Fig.2.7.In contrast.svstemswhosehi-shest ener,sy
occupiedbandis partiallvfilled areconductorsbecausethey havelittle spacing
amongtheiroccupiedand unoccnpied orbitals.
To form a senriconductor.onestarts',vithan insulatorasshownin Fig.2.gwith
its filled(dark)bandanda bandgapbetrveen thisbanclandits empty(clear.) upper
band.lf this insulatorrnaterialweresynthesizecl r,vitha smallamountof ,.dopant"
whose"'alenceorbitalshaveener-uies betu,een the fillecland emptybancisof the
tnsulator. onemavgenerate a semiconductor. If thedopantspecieshasno valence
electrons (i.e..hasan emptyvalenceorbitaly,it givesriseto an emptybandlying
betweenthe filledandemptybandsof the insulatoras shownin Fig.2.ga.In this
case.thedopantbandcanactasan electronacceptorfor electrons ercited(either
thermallvor by light) fiom the filled bandinro rhe dopantband.once ele*rons
enter the dopant band chargecan flow and the systembecomesa conductor.
Anothercaseis illustratedin Fig. 2.8b.Here,the dopanthasits own bandfilled
but lies closeto the emptybandof the insulator.Henceexcitationof electrons
from the dopantbandto the empty bandcan inducecurrentto flow.
2.3 Densitiesof statesin one, two, and three dimensions

W h e n a l a r g e n u m b e r o f n e i g h b o r i n go r b i t a l s o v e r l a p , b a n d s a r e
formed' However,the nature of these bands is very different in different
dimensions.
,-
!
The filled
and empty bands,the
band gap, and empty
acceptoror filled donor
oanos.
Beforeleavingour discussion ofbandsoforbitalsandorbitalenergiesin solids.

I wantto address the issueofthe densityofelectronicstatesandthe issueofrvhat
deternrines the energyrangeinto which orbitalsof a givenbandu,ill split.First.
lett recall the energyexpressionfor the one- and tr','o-dimensional
electronin a
box case,and let'sgeneralize it to threedimensions.The generalresultis
E:Lnlr2ti1(2mLj). (2.10)
where the sum over./ runs over the nurnberof dimensions(one,two. or three),
and L.1 is the length of the box along the 7th direction. For one dimensron,
one observesa patternof energylevelsthat grows with increasingn, and whose
spacingbetweenneighboringenergylevelsalsogrows.However,in tr,,r,o andthree
dimensions,the patternof energylevel spacingdisplaysa qualitativelydifferent
characterat high quantumnumber.
caseand,for simplicity,let'susea "box"
consider first the three-dimensional
that has equallengthsidesZ. In this case,the toral energyE is th2#l2nrL:1
times Qrl + nf, + n).fne latter quantitycan be thoughtof as the squareof the
lengthof a vectorR havingthreecomponents,?_r, nt,, ft:. Now think of three
cartesianaxeslabelednx,nt,,andn, andview a sphereof radiusR in this space.
The volume of the I /8 spherehavingpositivevaluesof ir.., r ,,,andn_-and having
D e n s i t i e so f s t a t e si n o n e ,t w o , a n d t h r e e d i m e n s i o n s 55
radiusR is ll8(4/3;rRr).Because eachcubehavingunit lengthalongtheilr, t'rr.,

and il, a-rescorrespondsto a singlequantumwave function and its energy.the
toralnumberl/,"'(6) of quantumstateswith positivefrx, n,., and n. and with
energybetweenzeroand E : (h2n2l2m L21R2is
:;(i"l#1")
i(]'-') (2",
The numberof quantumstateswith energiesbetr.r.een E and E + dE is
whichis thedensityQ(E) of states
(dilibrldE)dE, nearenergyE:
tl+ [tart:1"]r, ,).
o ,'-' : (t.12)
8\ ; " L ; = l a ' )
Noticethat this statedensityincreases as E increases. This meansthat,in the
three-dimensional case,the numberof quantumstatesper unit energygro$s;
in other words,the spacin-ubetweenneighboringstateenergiesdecreases, very
unlike the one-dimensional case rvhere the spacingbetweenneighboringstates
growsasn andthusE grows.Thisgrowthin statedensityin thethree-dimensional
caseis a resultofthe degeneracies andnear-degeneracies thatoccur.Forexarnple,
t h es t a t e w
s i t h n , , n . t .n. : : 2 . l . I a n d l . 1 , 2 , a n d 1 , 2 , I a r ed e g e n e r a taen.d
t h o sw e i t hn r . n \ .n. - : 5 , 3 . I o r 5 . 1 . 3o r 1 , 3 , 5o r 1 . 5 . 3o r 3 . 1 . 5o r 3 . 5 ,I a r e
degenerate andnearlydesenerate to thosehavingquantumnumbers4. ,1.I or l.
;1.:1.or 4. l. .1.
In the two-dimensional case.degereracies also occur and causethe density
ofstatesto possess an interesting6 dependence. In this case.we think ofstates
havingenergyE : (ti2ir2 l2m L21R:,butrvith Rl : rri + ni. The total number
ofstateshavinscnersvbetweenzeroand 6 is
, t ]nL: t
. \ . . . .: , rl r n - : t - t (2.ri)
\,r; )
E and E -t d E is
So, the densitl,of statesbeti.veen
e r E r+: + : + '( 1 r ' 1

LtL \ lf1- ,/
(2.14)
That is. in this two-dimensionalcase.the numberof statesper unit energyis

constantfbr high E valLres
('uvherethe analysisaboveappliesbest).
This kind of analysisfbr the one-dimensional casegives
( 2 l.s )
so the statedensitybetrveenE and E -t d E is

, . t'l
e r t ) : r r : . ( - J ! !)- u - ' , , . (2.16)
\ tr:T- /
which clearlyshowsthe lvideningspacing.and thus lowerdensity,as one goes
to higherenergies.
Two ls
orbitals combine to
produce a o bonding
and a o" antibonding
m o l e c u l a ro r b i t a l .
Thesefindingsaboutdensitiesof statesin one.trvo.andthreedimensionsare

irnportantbecause.in variousproblemsone encountersin studyingelectlonic
statesof extendedsvstemssuchas solidsand surfaces. one needsto knou,how
the numberof statesavailableat a siven total energy.Evariesll ith 6. clearlv. the
ans\ver to thisquestiondependsuponthedimensionality of the problem,andthis
fact is rvhatI lvantthe studentsreadingthis text to keepin mind.
2.4 The most elementarymodel of orbital energysplittings:

Hiickelor tight-bindingtheory
Nou'let'serarninewhatdeterrnines theenergyrangeinto which or-bitals (e.g, p"
orbitalsin polyenesor metals or p orbitalsin a solid)split.To begin.considertwo
orbitals.oue on an atom labeledA and anotheron a neighborinsatom labeled
B; theseorbitals could be. for example,the 1s orbitals of two hydrogenatoms.
such as Fig. 2.9 illustrates.However,the two orbitals could insteadbe til'o p"
orbitalson neighboringcarbonatomssuch as are showrrin Fig.2.l0 as they
form bondingand n* antibondingorbitals.In both of thesecases,we think of
formingthe molecularorbitals(Mos) @6as linearcombinations of the aronric
orbitals(Aos) x, on the constituentatoms,and we expressthis mathematicallv
as follou's:
, s-^
@^: ) Lr'.,Y,. (2.t7\
wherethe C1.,,orecalledlinearcombinationof atomicorbitalsto forn molecular

orbital (LCAo-Mo) coefficients.The Mos are supposedro be solutionsto the
Two atomic Schr<idinger equationin which the HamiltonianH involvesthe kinetic ener_ey of
p- orbitalsform a
the electronas well as the potentialsZ1 and zq detailingits attractionto the left
b o n d i n gz a n d
a n t i b o n d i n gz * and right atomic centers:
m o l e c u l a or r b i t a l .
H=-lil2ny2-rL*lq ( 2 .I 8 )
T h e m o s t e l e m e n t a r ym o d e l o f o r b i t a le n e r g ys p l i t t i n g s
57
In contrast,theAos centeredon the left atomA aresupposedto be solutionsofthe

Schrodinger equationwhoseHamiltonianis H : -/1?l2nty2 -f Vt,andtheAOs
onthe right atornB haveH : -h2 l2mV2 + Vn.Substitr.rting 0* :L.Cx.uXu
into the MO s Schrodinger
equationHQr : €rQr and then multiplyingon the
leftbythecomplexconjugateof x7,andintegratingoverther,0 andQcoordinates
of the electronproduces
(2.19)
Recall that the Dirac notation (a I b) denotesthe integral ofa* and 6, and (a loplb)
denotesthe integral ofa* and the operatorop acting on D.
In what is kno'uvnas the Hiickel model in organic chemistry or rhe tight-bin<1ing
model in solid-state theor1,,one approximates the integrals entering into the above
set of linear eqr-rations
as follows:
(i) The diagonalintesralt,X,,1-tt)

l2nY) + Li, + tr11X6)involvingthe AO centered
on thc right atomand labeled17,is assumed
to be equivalentto
-h! l2nV) * IrnlXr.),
(,X1, which meansthatnet attractlonoi-thisorbitalto the left
atomiccenteris neglected. Moreover.this integralrs approximated in termsof the
bindingenergv(denotedcr,not to be confuscdrviththe electronspinlirnctrona)
for an electrttnthat occupiesthe 17,orbital:|,y,,-li l2my) ,t l/plXr) = trr,.The
physicalrreaningof ar is thc kineticenergvof the elcctronin 17,plusthe
attractionof this elc-ctrorr to the'rightatomiccenter*,hileit residesin 17,.Of
coursc.an analoqous approximation is madefor the diagonalintegralinvoliing
x , , ; Q , , ) - / t : l 2 r n Y : + L ' r . 1 x ,-, ya , , .
(ii) The off-diagonalinregrals\xt,) - F l2nv. + ti + L\11x,,\1 areexpresserJ in
termsof a pararrerer rvhichrelatesto the kineticand potentialenereyof the
fJ,,.7,
elcctronu,hilcit reside-sin the "overlaprcgion"in which both X,,and X7,are
non-vanishing. This regionis shorvnpictoriailyin Fig.2. I 0 as the regionrvherethe
left and rieht orbitalstouchor overlap.The magnitudeof 13is assumed to be
proportionalto the ovcrlapS,,.7, betrveenthe two AOs: .t,.r,: e, I Xr,).lt turnsout
that f is usuallva negatir,,e
qr.rantity.
which can be seenby writing it as
(/.t,i-lt:l2ntv: + I\<1il i (,xr)t'tlx). Sincex,, is an eigenfuncrionof
-il 12ntV: a lzohavingthe eigenvaluea,,, the first term is equalto s, (a negauve
quantitv)tinres(X1,I X,,).the overlapS. The sccondquantity\Xr,ll/rlX")is equalto
the integfalof the overlapdensity17,Q.)tr"(r) multipliedby the (negative)
Coulorrrb potentialfbr attractir"e interaction of the electronwith the left atomtc
center.So.r,r'henever 17,(r.)and 1,,(r)havepositiveoverlap,p r.r'illturn out
negattVe.
(iii) Finally,in the mostelernentary I-ltickelor tight-bindingmodel,the overlap
integralst,X,,I ft,l - t,./, are neglectedand set equalto zero on the right sideof
the matrir ciqenvalueequation.However,in some HLickelmodels,overlap
betweenneiehboringorbitalsis explicrlvtreatc'dso in someof the discr.rssion
below '"veu'ill retain .!, ,,.
With theseHiickel approximations. the set of equationsthat determinethe

orbitalenergies €6 andthe corresponding LCAO-MO coefficients are\\'rit-
C'(.(?
ten for the trvo-orbital
caseat hand as in the first 2 x 2 matrix cquationssho\\'n
below:
[l f "i "' J] L[ c:l, l: ,tI. sl :r Jl[L:( I, { J (2 . 1 0

)
u,rittenas
*'hich is sor.netimes
| " - ' / r- . s .[1. . . ]- Ll nol . l ( 2 . 2I )

[ r - . s " - . . ]L . - . 1
of zerooverlapto
reduceu'ith the assulxption
Theseequations
[ " , . l [ , -=l . I ror l Ll I. 'ci l, ' ' l (2 . : 2)

Lf,"_L
l c*.1 L0
Thea parameters areidenticalif thetwo AOs x,, andXr,areidcntical.asr"'ould
be the casefor bonding betrveenthe tu'o ls orbitalsof lwo H atolltsor nt'o )11-
orbitalsof tu'o C atomsor tr.vo3s orbitalsof tr",oNa atoms.If the left and right
orbitalswerenot identical(e.g.,for bondingin Hel-l+or for the:r bondingirr a
C-O group).their o valueswould be differentand the Hiickel matrix problen.t
lr'ouldlook like:
[ " n l [ ' l : , I sr . ]l [ c I r l l i t
lf,"lLCo.l Ls LCRI
To find the MO energiesthat resultfrorn combiningthe AOs. one must find
the valuesof e for which the aboveequationsare valid. Takin-qthe 2 x 2 matrix
consistingof e times the overlapmatrix to the left-handside.the aboveset of
equationsreducesto Eq. (2.21). It is knou,nfrom trratrixal-uebra that sucli a set
oflinearhomogeneous equations (i.e.,havingzeroeson theright-handsides)can
havenon-trivialsolutions(i.e.,valuesof C that are not simplyzero)only if the
determinantof the n.ratrixon the left sidevanishes.Settingthis deteminantequal
to zero giles a quadraticequationin rvhichthe e valuesarethe unknor.vns:
(a-e):-(B-oS)r=0. (2.24)
This quadraticequationcan be factoredinto a product
( a - f - e * s S ) ( a+ P - €- s S ) : 0 . ( 2 . 2 )5
which hastrvo solutions
e:(a*p)/(l +S). and e = (a- F)l(l- S). (2.26)
As discussedearlieqit rums out that the B valuesare usuallynegative.so the

lor.restenergysuchsolutionis the e : (a * P)l0 + S ) solution,which givesthe
T h e m o s t e l e m e n t a r ym o d e l o f o r b i t a le n e r g ys p l i t t i n g s
qq
energyof the bondingMo. Noticethat the energiesof the bondingand antibond_

ing iVlos are not symmetricallydisplacedfrom the value a within this \.erslon
of the Htickelmodelthat retainsorbitaloverlap.In fact,the bondingorbitallies
lessthanp belowcv,and the antibondingMo lies morethanB abovea because
of the I * s and I - s factorsin the respectivedenominators.This asymmer-
ric lou.eringand raising of the Mos relativeto the energiesof the constituent
Aos is commonlyobservedin chemicalbonds;that is, the antibondingorbital
is more antibondingthan the bonding orbital is bon<iing.This is ar.rother im-
portantthing to keep in mind becauseits effectspervadechemicarbondins and
spectroscop)'.
Havingnotedtheeffectof inclusionofAo overlapeffectsin the Hiickel moder,
I shouldadmit that it is far more commonto utilize the simplifieciversionof the
Hiickelmodelin which the s factorsareignored.In so doing,oneobtainspatterns
of N'Ioorbitalenergiesthat do not reflectthe asymmetricsplittingin bonding
and
antibondingorbitalsnotedabove.However.this simprifiedapproachis easier
to
useand ofl'ersqualitativelycorrectMo energyorderin-es. So, let'sproceedwith
our discussion of the Hiickelmodelin its simplifiedversion.
To obtainthe LCAo-Mo coerfcientscorresponding to the bondingandanti-
bondingMos. onesubstitutes thecorresponding a valuesintothelinearequarrons
f";'.1,]tr]:t:]
andsoh'esfor the C,,coefficients(actually,onecan solvefor alr but one c',,.and
t1)1\
thenusenorrnalizationof the Mo to deterrninethefinal c,, ). Forexample.for the

bondingN,lO.lve substitutee : a * B into theabovematrixequationandobtain
two equationsfbr C1 and Cp:
-fCt-t
dCn:0. ( 2 . 2)8
IJCL-pcR-0. 12)9)
Thesetr.voequations areclearlynotindependent;
eitheronecanbe solvedfor one
C in termsof the otherC to sive
Cr = Cn. (2.-r0)
which means that the bonding MO is
Q:CJxr*xil. (2.31)
Thefinalunknor,vn, C1,is obtainedby notingthat@is supposedto bea norrnarized
function (A I A) : l. Within this versionof the Hrickel
model, in which the
overlaps is neglectedthe normalizationof leadsto the
@ followine condrrion:
| : @ | d ) = C l ( t , x t lx L )+ ( x R x R :) ) 2 C l .
AN M o d e l p r o b l e m st h a t f o r m i m p o r t a n ts t a r t i n gp o i n t s
with the final resultdependingon assumingthateach1 is itselfalsonormalized.

. e k n o wt h a tC 1 : 1 1 l 2 ) l : . a n dh e n c et h e b o n d i n gM O i s
S o ,f i n a l l y w
O:,ll2)t' er+x*) rl l'li
A c t u a l l yt.h e s o l u t i o no f I : 2 C ' i c o u l da l s oh a v ey i e l d e dC ' r : - ( l / 2 ) 1 t 2 a n d

then vr,ewould have
O: - , l t l 2 ) t t . ( x r* x n ) (2.3.1)
Thesetwo solutionsarenot independent (oneisjust - I tinresthe other).so only

one shouldbe includedin the list of MOs. Horvever. eitherone is just as goodas
the otherbecause. as shownvery earl1,in this text.all ofthe ph1'sical properties
that one computesfrom a wave function dependnot on ry'but on r/r*{r. So. tu,o
u'avefunctionsthat differ from one anotherby an overallsign factor.as u,ehave
here,haveexactlythe sar.nerlr*tb andthus are equivalent.
ln like fashion.we cansubstitute€ : cr - p into the matrix equationandsolve
for the C1 and Cp valuesthat are appropriatefor the antibondingMO. Doing so
glvesus
i)
Er : 1t121 (xr - Xr.) (2.3
5)
or. alternatively.
O " : ( l l 2 l t ' 2 ( X*n X r ) . (2.36)
Again. the fact that either expressionfor @* is acceptableshowsa property of

all solutionsto any Schrodingerequations;any multipleof a solutionis alsoa
soiution.In the aboveexample,the two "answers"for @*differ by a multiplicative
factorof(-1).
Let's try anotherexampleto practiceusing Hiickel or tight-bindingtheory.In
particular,I'd like you to imagine two possiblestructuresfor a clusterof three
Na atoms(i.e.,pretendthat someonecameto you and askedwhat geometryyou
think sucha clusterwould assumein its ground electronicstate).one linear and
onean equilateraltriangle.Further,assumethatthe Na-Na distancesin both such
clustersare equal(i.e.,that the personaskingfor your theoreticalhelp is willing
to assumethat variationsin bond lengthsarenot the crucialfactor in determining
which structureis favored).In Fig.2.ll, I showthe two candidateclustersand
their 3s orbitals.
L i n e a ra n d
e q u i l a t e r at rl i a n g l e
structuresof sodium
Inmer.
T h e m o s t e l e m e n t a r ym o d e l o f o r b i t a le n e r g ys p l i t t i n g s o l
NumberingthethreeNa atoms'valence3s orbitalsh, X2,and X3,we thenset

up the 3 x 3 Htickel matrix appropriateto the two candidatestructures:
[ " oe po ll (2.31)
l p
Lo P d)
for the linear structure(n.b.,the zeroesarisebecause11 and Xj do not overlap
and thus have no p coupling matrix element).Alternatively,for the triangular
structure.we find
[ " p e 1
l P" P l (2.38)
L Pp " )
as the Hiickelmatrix.Eachof these3 x 3 matriceswill havethreeeigenvalues
thatwe obtainby subtractinge from their dia_eonals
and settingthe determinants
ofthe resultingmatricesto zero.For the linearcase,doing so generates
(a*e)r -2ft(o -e):0, (2.3e)
and for the trian_qlecase it produces
{ o - r ) ' - 3 d : ( o- e ) + 2 d r : 0 (:..10)
The first cubicequationhasthreesolutionsthat give the MO energies:
s:cv*(2)r:f,. F:(r. and r=d-(21tr..U, (:.,11)
for the bonding.non-bondingand antibondingMOs, respectively.

The second
cubicequationalsohasthrecsolutions
t::a*2f. s:a-fl. and e:u-8. (2 . 4 2 )
So.for the linear and triangularstructures,the MO energypatternsare as shou'n

tn rls. l. Il.
- a - Q)1/2p
-c-B
Energy
o r d e r i n g so f m o l e c u l a r
- a + (z)tt2| o r b i t a l so f l i n e a r( l e f t )
a n d t r i a n g u l a r( r i g h t )
-c+2p s o d i u mt r i m e r s .
62 M o d e l p r o b l e m st h a tf o r m i m p o r t a n ts t a r t i n gp o i n t s
Forthe neutralNa: clusteraboutr".hichvou wereaskedyou havethree'u'alence

electronsto distributeamongthe lowestavailableorbitals.In the lincarcase.we
placetr'"'oelectronsintothe lowestorbitalandone into the secondorbital.Doing
s o p r o d u c c s a t h r c e - e l e c t r o n s t a t e wei trhr retrogtluo6lf : l t u + l ' l , ' l ) + o :
3cv* 2 2t i2B. Altematively,for the triangularspecies.we put trvo electronsinto
the lowestMO and one into eitherof the degenerate MOs resultingin a three-
electronstatewith totalenergl'E :3a f 38. Becauseli is a uegativequantitv.
thetotalenergyofthe triangularstructureis lowerthanthatofthe linearstructure
r
s f n c c - i> I l
^ l -1 .
The aboveexampleillustrates how we canuseHtickel"tight-binding theor)to

makequalitativepredictions(e.g..which of trvo"shapes"is likel.vto be of lor"'er
ener'-uy).
Noticethat all one needsto knou'to apply'sucha model to any set of
atomicorbitalsthatoverlapto form MOs is:
(i) theindividual a (whichrelatcto theelectronegativitv

AO energies of theAOs)and
(ii) thedegreeto whichtheAOscouple(theB pararreters
*'hichrelateto AO or,eriaps).
Lett seeif you can do someof this on your own. Using the aboveresults.
uould you expectthecationNai to be linearor triangular? What abouttheanron
Na.,? Next. I u,antyou to substitutethe MO enersiesback into the 3 x 3 matrix
andfind the C1. C2,and C3 coefficients to eachof the threeMOs of
appropriate
the linearand ofthe triangularstructure.Seeifdoing so leadsyou to solutions
that can be depictedas shor,l'n
in Fig.2.l3" and seeif you can placeeachsetof
MOs in the properenergyordering.
@
The
(-a-a-\
\_\v
orbitalso{
l i n e a ra n d t r i a n g u l a r
s o d i u mt r i m e r s( n o t e ,
they are not energy
ordered).
T h e m o s t e l e m e n t a r ym o d e l o f o r b i t a le n e r g y
splittings
bJ
Ethylene
with four C-H
bonds,one C-C o bond,
and oneC-C z bond.
No'v. I want to showyou hor'vto broadenyour horizons

and usetight-binding
theoryto describeail of the bondsin a more compricated
moleculesuch as
erhvleneshownin Fi-e'2.14. within the moder described
above, eachparr ot'
orbitalsthat "touch" or overlap-9ivesrise to a 2 x 2 matrix.
More correctry,ail
n of the constituentAos form an n x n matrix, but this
matrix is brokenup rnro
2 x 2 blockswhenevereachAo touchesonly one
otherAo. Noticethatthis did
not happenin the trian-uularNa3casewhereeachAo touchedtwo otherAos.
For
the ethylenecase,the valenceAOs consistof (a) fbur
equivalentC sp: orbitals
that are dire*ed towardthe four H atoms.(b) four
H ls orbitals,1c)t*.o c spr
orbitalsdirectedtowardone anotherto fo'n the
c-c o boncl and (d) two c p.,
orbitalsthatwill forn.rthec-c z bond.This totar
of l2 Aos generates six Hticker
matrcesas shor.vn bero*,:we obtainone 2 x 2 matrix for the c-c
o bondoi-the
form
o.o, d.o,.o,-l
I (2..13
)
| 1,n,..0, a,o, J
and one 2 x 2 matrix lor the C-C z bond of rhe
form
[ ",' r)r,,.]
(l -+4)
lfo. w "n. l
Finally.we alsoobtainfour identical2 x 2
n.ratrices
fbr the c-H bonds:
r -
| 0,p, l,n,.n 1
Q'45)
Lp.n,n ", J
The above marricesrvill then produce (i)
four identical C_H bondin_e MOs
h a v i n g e n e r g ie e :s t / 2 { ( a , * r y c ) _
[ ( a H_ a c ) : * 1 p 2 l r , z ] , f i i i i o u . : a . n t . u f
C-H antibondingMOs havingenergiest* :
I/21@u * a6) f [(ns _ oc)r +
4 7 2 l t i 2 | , ( i i i ) o n e b o n d i n gC - C r o r b i t a l
with E:epr + fl, (iv) a parrner
antibondin-eC-C orbital with e* : dp, _
F, &) a C_C o bonding MO with
t : ospr* p ' and(vi) its antibonding partnerwith e* - cy,pr p. tn att of these
expressions.the B parameteris supposed
to be that appropriateto the specific
orbitalsthat overlapas shownin the matrices.
64 M o d e l p r o b l e m st h a t f o r m i m p o r t a n ts t a r t i n gp o t n t s
If you wish to practicethis exerciseof breakinga lar_ue rnoieculedown into

setsof interactingAos. try to see what Hiicker matricesy.ou
obtain and r.,,tat
bondingand antibondingMo energiesyou obtain for the 'alence
orbitalsof
methane s h o w ni n F i g .2 . 1 5 .
Beforeleai'ingthis discussionof rhe Hrickerrti_cht-binding nroder.I needto
stressthat it has its ffar.vs (becauseit is basedon approximations and rnvolves
neglectingcertainterms in the Schrcidinger equation).For example.it predicts
(seeabove)thatethylenehasfour energeticallv identicalc-H bondingMos (and
four degenerate c-H antibondingMos). Hou,ever, this is not what is seenwhen
photoelectron spectraare usedto probetrreenergies
Methane of theseMos. Likeu,ise.it
m o l e c u l ew i t h f o u r C * H suggests thatmethanehasfour equivalent C-H bondingandantibonding orbitals.
o on o s . r,''hichagainis not true.It turnsout that.in eachof thesetwo
caseslethyleneand
nrethane). theexperiments indicatea groupingof four ilcarlr.iso-ener_qetic bond_
ing Mos andlour nearryiso-energetic antibonding Mos. Horve'cr.thereis some
"splitting"
amongtheseclusrersof four Mos. The splittingscan be interpreted,
within the Hrickelmoder.as arisingfrom couplirgsor interactions
anron_c. for
example.onesp2or sp3orbitalon a givenC atomandanother
suchorbitalon the
s a n r ea t o m .S u c hc o u p l i n u cs a u s et h e , v r r H L i c k eml a r r i xt o
n o tb l o c k _ p a r r i r i o r r
lnto groupsofl x 2 sub-matrices because no*.thereexistoff-diagonalp factors
thatcoupleonepairof directedAos to another. when suchcouplingsareincluded
in the analysis.one findsthatthe clustersofN{os expected
to b.,l.g.nerate are
not. but aresplitjustas thephotoelectron datasuesesr.
2.5 Hydrogenicorbitals
The hydrogenicatom problem forms the basis of much
of our thinking
about atomic structure.To sorvethe correspondingschrodinger
equation
requiresseparationof the r, 0, andg variables.
The Schrcidinger equationfor a singleparticleof nass p movi'g in a central

potential(one that dependsonly on the radial coordinate
r) can be written as
_-
li 1 a: a: a:\ .--.-\
I I -l- +
+ l - l , r , t Ir '/l ( r :' -L- -:+ ' r 2 + : : ) t l t: E l t ' e46)
2g \ 3:i2 ail o = t) ' l ' +
or, introducingthe short-handnotationV2:
-lt2
/2mY2p * Illt = Ep (2.47)
This equationis not separablein Cartesiancoordinates(x,,i,,:) becauseof the
way r, 1', and ; appeartogetherin the squareroot. However.
it is separablei'
sphericalcoordinateswhereit hasthe form
-- !, w . [ a / . . , a / \ l * I a t. a/\ t d:t
L; \'-;/J ;,*, ( ' ' " ,* i - _ . * ; # - r r , ' t , t '
- - t i / 2 r n v : g+ v { / : E V
(2 . 4 8 )
H y d r o g e n i co r b i t a l s
o5
Subtractingv(r)(r fron both sidesof the equationand multipryingby -2{i

thenmoving the derivativeswith respectto r to the right-handside.one-obtalis
I U / a/i \ | A:,IJ 2ur)
-#rt - Itu'tlr- lt ( ,' #)
d r Il * *i a #:
-:- sintt*--|
s, nd H|\ #
(2.+e)
Noticethat,exceptfbr ry'itsell the right-handside of this equationis a functron
ofr only; it containsno d or @dependence. Let's call the entireright-handside
F(rlrL to ernphasizethis fact.
To furtherseparatethe d and@dependence, we multiply by sin?g andsubtract
rhed derivativeterms from both sidesto obtain
:F(,")ry' o - sinoj_*(.'"r#)
sinr (2.s0)
#
Norv we have separatedthe @ dependencefrom the 0 andr
dependence.we
now introducethe procedureusedto separatevariablesin differentiar
equations
and assumery' can be written as a function of times a function
@ of r) and0:
,lr : A@)Q(r.0). Dividin_eby Oe, we obtain
t
* # : ( o , s i nt2) e -s i n e G
$
'"r#)) (2.51)
Now all ofthe / dependence is isoratedon the left-handside;the right-handside

contalnsonly r andd dependence.
wheneverone hasisolatedthe entiredependence on onevariabreas we have
doneabovefbr the @dependence. one can easilyseethat the Ieft- and right-hand
sidesof the equationmust equala constant.For the above
exampte.thetert-
handsidecontainsno r or g dependence and the right-handsidecontainsno p
dependence. Becausethe two sidesare equal,they both must actualiycontain
no
r,0, or @dependence; thatis, theyareconstant.
For the aboveexample,we thereforecan set both sides
equarto a so-called
separation constantthat we call -m2.lt will becomeclearshortlywhy
we have
chosento expressthe co'stant in the form of minus
the squareof an integer.
You may recallthat we stucliedthis same equatron
@ earlierand learnedhow the
integerrr arisesvia the boundarycondition that
Q andQ * 2z representidentical
geometries.
2 . 5 . 1T h e O e q u a t i o n
The resulting@ equationreads(the "symbor is usedto
representsecondcreriva-
tive)
o"+t1:o:o (2.52t
This equationshouldbe familiarbecauseit is the
equationthatwe trearedmuch
earlierwhenwe discussedthe:-component of angularmomentum.So.its further
oo M o d e l p r o b l e m st h a t f o r m i m p o r t a n ts t a r t i n gp o i n t s
analysisshouldalsobe familiar.but, for completcness.

I repeatmuch of it. The
aboveequationhasas its mostgeneralsolution
tnlr) ( 2 . 5)3
Q = Ae""Q + Be
Becausetlrervavefunctionsof quantummechanics representprobabilitydensi-

ties.they r.nustbe continuousand single-valued.
The lattelcondition,appliedto
our <Dfunction.meansthat
O(d):Q(2;t*4tl r r 5 4l
. 1 e i " " 1 ' (-l ' J r i n t ,+' B e i * a ( l - c : " " - ; : g. (2.5-5)
This conditionis satisfied only whentheseparation constantis equalto an integer

m : 0 , + 1 . + 2 . . . . a n dp r o v i d e sa n o t h eer x a m p l eo f t h e r u l e t h a l q u a n t i z a t i o n
comesfrom the boundarycor.rditions on the r.vavefunction. llere nr is restricted
to certaindiscretevaluesbecause the wavefunctionmustbe suchtl.ratwhenyou
rotatethrough2:r aboutthe :-axis. you must get back \\4ratyou startedvn,itl.r.
2 . 5 . 2T h e O e o u a t i o n
Norv returningto the equationin which the @dependence was isolatedfrom the
r and0 dependence and rearrangingthe 0 termsto the left-handside,rve have
1 ii / dO\ nr:O
- : Ftr)Q (2.-56)
""p a6 \sin6-i/ *t
In this equationwe haveseparated
0 andr variationssowe canfurtherdecompose
tlrewavefunctionby introducingQ : O(6)R(r), which yields
1 1 at r)G)\ lrl FtrtR

l s i n 6 -l- *: ^ =-i.
O ri"B ap \ do/ sln-H ^
where a secondseparationconstant,-),, has been introducedonce the r and

0 dependentterms have been separatedonto the right- and left-hand sides,
respectively.
We now can write the d equationas
##(''",#)-#--,(,, ( 2 . 5)8
wheren is the integerintroducedearlier.To solvethis equationfor O, we make

z : cosI and P(z) : O(9), so JT -= : sind, and
the substitutions
0 020 . d. -, d
= -sln (2.59l,
Ae 60 0z dz
H y d r o g e n i co r b i t a l s ot
Theran-qeof valuesfbrd was0 < I < z, so the rangefor: is -l < : < l. The
equationfbr O, whenexpressedin termsof P and:. becomes
I / ,/Pt ,r,]P
- l r l - -r r--- l (2 . 6 0
21"-='E)-t--=t-)'P:o )
Noi.r'we can look for polynomial solutionsfor p, because: is restrictedto be

lessthanunity in magnitude.lf m :0. we first let
p -- f . , - r
/-"t- (2.61)
t=1)
intorhedifferential
andsubstitute equationto obtarn
-
\-rl - 1 ) r l . J - l rl ,t r , - : -I - ' - L
\ - ,. f, L l ,l .k, t r l : "- ; f
/-,"'-',', t t . : a= 0 . (2.62)
{=1,
Equatinglike powersof ; gives
ttt(k(k]_l)-^\
( 1 . 6 i)
Note that for lar_sc-

valuesof l
,,^_,- tr(t+i) _,
,k (2.64)
fr,(l+i)(r+i)-'
Sincethe coefhcicntsdo not decrease with f for larget. this serieswill diverge
for-- : *l unlessit truncates at finiteorder.This truncationonly happensif the
separatron constanti obe-v"s ), : l(l * l). where/ is an integer.So. onceagtin.
we seethata boundarvcondition(i.e..thatthe wavefirnctionnot diverge
andthus
be normalizable in this case)gil'esriseto quantization. In thiscase.the valuesof
i arerestricred to 1(/ * I ): before.we sawthat,r is restricted to 0. * l. +2. . . .
Sincethe'above recursionrelationlinkseveryothercoefflcient. we canchoose
to solvefor the evcnand odd functionsseparately. choosingd1,and thendeter-
miningall of the evenr1rin termsof this,q,. fbllor^,ed by rescalingall of these
ar to lrakc the functionnormalizcd. generates an e\.ensolution.choosinga7and
determiningall of the odd a1 i' like rnannereenerates an odd solution.
For / : 0. the seriestruncatesafter one term anclresultsin po(:) : L For
/ = I t h es a m et h i n ga p p l i e as n d p 1( : ) : ; . F o r1 - 2 . a t : _ ' 6 + : _ 3 a o
, so
o n e o b t a i n sP : : 3 2 ) - l . a n d s o o n . T h e s ep o l y n o m i a l ,s. . . . l l . d
Legenclre
polvnominls.
For the more generalcasewherem I 0. one can proceedas aboveto gener-
atea polynomialsolutionfbr the o function.Doing so resultsin the
followine
solutions:
- ,,, ",.1,,) tp.t -\

t \ - l
I > t ' t t _ r _ t t _ l , i
| | t- t - \ r
- _ ./ (2.(,5)
d:tnt
o.J M o d e lp r o b l e m st h a t f o r m i m p o r t a n ts t a r t i n gp o i n t s
Thesefunctionsarecalledassociated Legendrepolynomials. andtheyconstitute

the solutionsto the O problemfor non-zerorr r.'alues.
TlreaboveP andei''4'functions. whe're-expressed in termsof 0 and@.yield
thefull angularparrofthe wavefunctionfor anycentrosymmetric potential.These
tQ exp(inrQ),and
Q): pi,,rcose)er)
solutionsare usualll,written as Y1.,,,(0.
arecalledsphericalharmonics.Theyprovidethe angularsolutionof the (r. 0. d)
Schrodinger equationfor anl problemin rvhichthepotentialdepends onl1,sn 11-r.
radialcoordinate. Suchsituationsincludeall one-electron atomsand ions ie.g.,
H, He*, Li*+. etc.).the rotationalmotion of a diatomicrnolecule(u,herethe
potentialdepends only on bondIengthr). themotionof a nucleonin a spherically
symmetrical "box" (as
occursin the shellmodelof nuclei).andthe scattering of
two atoms(u'herethe potentialdependsor.rlyon interator.llicdistance).The [.,,,
functionspossessr,aryingnumbersof an-{ularnodes.u,hich.as noted earlier.
give clear signaturesof the angular or rotationalenergy content of the wave
function.Theseangularnodesoriginatein the oscillatorynatureofthe Legendre
and associated Legendrepolynomialsp,"'(cosd);the higher/ is. the more sign
changesoccurwithin the polynomial.
2 . 5 . 3T h e F e q u a t i o n
Let usnowturnour attentionto theradialequation, whichis theonlyplacethatthe
explicitform ofthe potentialappears.Using our earlierresultsfor the equatlon
obeyedby the R(r) functionand specifyingv(r) to be the coulomb potential
appropriatefor an electronin the field of a nucleusof charge*Ze, yields
l d /.dR\ f2u/_ Z e z \ t ( t+ t t l r
Ft\'-,1,)+Lf\";)- .: Jn:o {266)
we cansimplify thingsconsiderablyifwe chooserescaledlengthandenergyunits
becausedoing so removesthe factorsthat dependon p,li,and e. we introducea
new radial coordinatep anda quantityo as follows:
,, 7) .,1
, : (-t:u \i ,-. , ) F Z C
\ r / \ 2 . 6 7)
2Ett
Noticethat if E is negative,asit will be for boundstates(i.e..thosestateswith en-
ergybelowthatof a freeelectroninfinitely far from thenucleusandwith zerokin-
etic energy),p is real.on the otherhand,if E is positive,asir will be for statesthat
lie in the continuum,p will be imaginary.Thesetwo caseswill give riseto quali-
tativelydifferentbehaviorin the solutionsofthe radialequationdevelopedbelow.
We now definea function S suchthat S(p) : R0.) and substituteS for R to
obtain
i j ; G f l . ( - i- ' # + 1 ) s : o (2.68)
H y d r o g e n i co r b i t a l s 69
The differentialoperatortermscan be recastin severalways using

I ,/ / .,/S\ d2s zds I d1
- (2.69)
;-.T ,,tpS).
,t,tr\tO)= ap- pLtp pLlp-
The strategythat we norv follow is characteristicof solving secondorder

equations.we will examinethe equationfor s at large and small p
diff-erential
values.Havingfound solutionsat theselimits,we will usea powerseriesin p to
"interpolate"bet'"veen thesetwo limits.
Let us begin by examiningthe solutionof the aboveequationat small values
of p to seehow the radial functionsbehaveat smallr. As p + 0. the secondterm
in thebracketsin Eq.(2.68)will dominate.Neglectingthe othertwo termsin the
brackets.we find that,tbr srnallvaluesof p (or r ), the solutionshouldbehavelike
pL andbecausethe tunctio'must be normalizable. we must haver > 0. Since
z canbe any non-negativeinteger.this suggeststhe followin-emoregeneralform
for S(p):
S(p) x pLe-u1 (2.70)
Thisform rvill insurethatthefunctionis normalizable sinceS(p) * 0 asr * eq,

forall l, as long as p is a realquantity.If p is imaginary,sucha form may not
be normalized(seebelowfbr turtherconsequences).
Turningnow to the beha'ior of s for largep. rvemakethe substitutionof .!(p)
intotheaboveequationandkeeponlv thetermswith the largestporverof p (e.g.,
thefirstterm in bracketsin Eq. (2.68)).Upon so doing.rveobtainthe equation
a2pt g un: o ",' t : . 7| )

!o''
whichleadsusto concludethattheexponentin thelarge-pbehaviorof s i. u : j.
Havingfbundthe small-and large-pbehaviors of s(p), we cantakes to havethe
followingform to interpolatebetrveen
largeand smallp-values:
S (p ) : p L e - / ' t 2P 1 p 1 . \/-.tL)
wherethe function P is expandedin an infinite powerseriesin p as p(p) :

Lorpr. Again substitutingthis expressionfor S into the aboveequationwe
obtain
P " p+ P ' ( 2 1 t 2 - o l * P ( o- Z - l ) : 0 ra 7l I
andthensubstituting the powerseriesexpansion of p andsolvingfor theai,swe

arriveat a recursionrelationfor the ai. coefficients:
(A-o*L+l)at
(2.71)
(r+l)(ft+21+2)
For largek, the ratio of expansioncoefficientsreachesthe limit ar,+r at : I k.
I I
which has the samebehavioras the power seriesexpansionof ep. Becausethe
po$'erseriesexpansion of P describes a functionthatbehaves like e/,fbr largep.

the resultingS(p) functionvr'ouldnot be nonnalizablebecausetlree-pr'l factor
would be overw'helmed by this e/' dependence. Hence.the seriesexpansion of p
must truncatein orderto achievea normalizable"! function.Noticethat ilp is
imaginarv.as it rvill be if E is in the continuum.theargumentthattheseriesrnust
truncateto avoidan exponentiallvdii,er-sing functionno longerapplies.Thus.
we seea key differencebetu'eenbound lwith p real) and continuum(u,ith p
imaginary)states.In the formercase.the boundarvconditionof non-dirersence
arises:in the larter.it does not becauseexp(p/2) does not divergeif p is
rmaginary.
T o t r u n c a t e a t a p o l y n o moi a
f ol r d e r n ' .w e m u s t h a vne, - o + L + I = 0 . T h i s
impliesthatthe quantityo introducedpreviouslyis restrictedto o- : n' t L * l.
which is certainlyan integer;let us call this integern. If u,elabelstatesin order
o f i n c r e a s i nng : 1 . 2 . 3 . . . . . w e s e et h a td o i n - s o i s c o n s i s t e nwt i t h s p e c i f y i n g
a r n a x i m u mo r d e r( n ' ) i n t h e p ( p ) p o l y n o m i anl ' : 0 . l . 2 . . . . a f t e ru , , h i c thh e
l-value canrun from Z : 0, in stepsof unity.up to I : n _ 1.
Substituting the integern for o, we find that the energylevelsarequantized
because o is quantized(equalto l):
- ' J
.f : _:-;__;
llL-c
{-./t }
:IT II.
and the scaleddistanceturnsout to be

Zr
(2.761
aorl
Here,the lengthas is the so-calledBohr radius(ao : li2 ,rnz);it appearsoncethe

1
aboveexpressionfor f is substitutedinto the equationfor p. Using the recursion
equationto solve for the polynomial'scoefficientsa1,for anychoiceof r and /
quantumnumbersgeneratesa so-calledLaguerrepolynornial;p,,_1_1(p).They
containpowers ofp fromzerothroughn - L - l. andtheyhaver - r - I sign
changesas the radial coordinaterangesfrom zero to infinity. It is thesesign
changesin the Laguerrepolynomialsthatcausethe radialpartsof the hydrogenic
wavefunctionsto haven - L - 1 nodes.For example,3d orbitalshaveno radial
nodes,but 4d orbitalshaveone;and as shownin Fig. 2.16.3p orbitalshaveone
while 3s orbitalshavetwo. once again,thehigherthe numberof nodes.the hieher
the energyin the radial direction.
Let me again remind you about the dangerof trying to understandquantum
wave functions or probabilitiesin terms of classicaldynamics.what kind
of
p o t e n t i azl ( r ) w o u l d g i v e r i s e t o , f o r e x a m p l e , t h e 3 s p ( r ) p l o t s h o w n i n F i g . 2 . l 6 ?
classical mechanicssuggeststhat p should be large where the particle moves
slowly and small where it movesquickly. So, the 3s p(r) plot suggeststhat the
radialspeedof the electronhasthreeregionswhereit is low (i.e.,wherethepeaks
in P are)andtwo regionswhereit is very large(i.e.,wherethe nodesare).
This.in
H y d r o g e n i co r b i t a l s
t l
€
!
Plotsof the
r a d i a lp a r t so f t h e 3 s a n d
3p orbitals.
turn,suggests thattheradialpotentialz(r) experiencecl by the 3s erectronis high

in threeregions(nearpeaksin p) and low in two regions(and
at thenucreus). of
course.this conclusionaboutthe form of v(r) ls nonsense
and againillusrrates
how one must not be drai.vninto trying to think of the
classicalmotionof the
particle.especiallylor quantumstateswith small quantum
number.In fact,the
low quantumnumberstatesof suchone-electron atomsand ionshavetheirradial
P(r) plots focusedin re-qions of r-spacewherethe potential-Ze2
1r is most
attractive(i.e..lar_gest in magnitucle).
Finally.we notethatthe energyquantization doesnot arisefor stateslylng in
the continuumbecause the conditionthat the expansionof p(p\terminatedoes
n o ta r i s eT. h es o l u t i o ncsl f t h er a d i ael q u a t i o a
n p p r o p r i a treor h . s . s c a t r e r i nsgr a t e s
(which relateto the scattering motionof an electronrn the field of a nucleusof
chargeZ) area bit outsidethe scopeof this text. so we will
not treatthem further
here. For the interestedstudent,they are treatedon p.
90 ofthe text by Eyring,
Walter,and Kimball.
To review separationof variableshas been used to solve
the fulr (r. {), Q)
Schrridinger equationfor oneelectronmovingabouta nucleusof chargeZ.The
0 andQ solutionsarethe sphericalharmonicsyt.,,(0,@).The
bound-state radial
solutions
R , , . 7 Q ): S ( p ) = p L s - r ' / 2P , - r - r ( p ) (2.77\
dependon the ir and / quantumnumbersand are given in terms
of the Lasuerre
polynomials.
tz M o d e l p r o b l e m st h a t f o r m i m p o r t a n ts t a r t i n gp o t n t s
2 . 5 . 4S u m m a r y
To sunrmarize. the quantumnumbersL and, nt arisethroughboundaryconditions
r e q u i r i n g t l t a t i l t (b0e) n o r m a l i z a b r e ( i . e . " n o t d i v ear n
g ce l)t t r ( 4 t r : t / r ( 4 t t 2 r \ .
The radialequatio'.which is theo'ly pracethe potenriarenergy
e'ters.is found
to possess bothboundstates(i.e..statcswhoseenergieslie belou.theasynrptote
a t * h i c h t h e p o r e n r i ar a l r r i s h easn d t h e k i n e r i ce n e r g li s z e r t r c) ' d
conlirrruni
stateslying energeticalll, abovethis asynrptote. The resultinglryclroeenic u,ave
f u n c t i o n s( a n g u l aar n d r a d i a r ) a n de n e r g i eas r es u n r m a r i z e d p p .
on 1 3 3 - r 3 6i n
the text by Paulingand Wilsonforr up to anclincluding6
anclI up to -5.
There are both bound and continuumsorutionsto the radiar
Schrcidinger
equationfor the attractivecoulornb potentialbecausc.at cnelgies
bel,r.r,, the
asymptote. thepotentialconfinestheparticlebetweenr : 0 andan outer
turnin_9
pornl.whereasat energies abovetheasymptote. theparticleis no longerconfined
b v a n o u t e rt u r n i n gp o i n t ( s e eF i g . 2 . r 7 ) . T h e s o l u t i o n s
ofthis one-electron
proble'r fornr the qualitativebasisfor n.ruchof atomic
and nrolecularorbital
theory.For this reason.the readeris encouraged to gain a firr.rerunclerstandin_r
ofthe natureofthe radialandangularpartsofthese*,avefuncrions.
The orbitals
thatresultarelabeledb,vn. L. and,r quantur,nurnbersfor
the lroundstatesand
by z and,,r quantumnumbersandthe energy6 for the continuur.n
states.Much
as theparticle-in-a-bor orbitalsareusedto qualitatively clescribe z-electronsin
conjugatedpolyenes,theseso-calledhydrogen-like orbitalspro'ide qualitative
descriptions of orbitalsof atomswith nrorethana singleelectron.By introducing
the conceptof screeningas a way to represent the repulsiveinteractions among
the electronsof an atom,an effectivenucrearchargeZsl.ca.be
usedin placeof
Z inthe rfln.1.n,.<nd 8,, to generateapproximate atomicorbitalsto be filled by
electronsin a rnany-electronafom. For example,in the
crudestapproximation
ofa carbonatorn,the two rs electronsexperiencethe full
nuclearattractionso
Zen:6 for them,whereasthe 2s and 2p electror.rs are screened by the two ls
-r"a,,'l
0.0
'-"1
Radial
potentialfor hydrogenic
a r o m sa n d b o u n da n d
c o n t i n u u mo r b i t a l
energies.
Electron
tunnelino 73
electrons,so 2"6 : 4 for them. Within this approximation,one then occupies

nvo 1sorbitalswithZ:6, two 2s orbitalswith Z:4 and two 2p orbitalswith
z - 4 in formingthe full six-electronwavefunctionof the lowestenersvstateof
carbon.
2.6 Electrontunneling
T u n n e l i n gi s a p h e n o m e n o n o f q u a n t u m m e c h a n i c s ,n o t c l a s s i c a lm e c h a n -
ics. lt is an extremely important subject that occurs in a wide variety of
chemicalspecies.
Solutions to the schrodinger equation display several properties that are very
different from what one experiences in Newtonian dynamics. one of the most
unusual and important is that the particles one describesusing quanfum mechanics
can move into regions of space where they would not be "allowed" to go if they
obeyedclassicalequations.Let us consicleran example to illustratethis so-called
tunneling phenomenon. Specifically, we think of an electron (a particle that we
likely would use quantum mechanics to describe) moving in a direction we will
call R under the influence ofa potential that is:
(i) Infinitefbr R < 0 (thiscoulclfor example.represent a regionof spacervithina

solid materialrvherethe electronexperiencesvery repulsiveinteractions,,vithother
electrons ):
(ii) constanta'd ne-eative for somerangeof R betrveenR : 0 and R,,,",(this could
represent the'attractiveinteraction
of the electronswith thoseatomsor molecules
in a finiteregionof a solid):
(iii) Constantand repulsiveby an amountAI/ + D" fbr anotherfinite region
frorn R*o,
to R,"a^+ d lthis could representthe repulsiveinteractionsbetrveenthe electrons
and a layerof moleculesof thickness6 lying on the surfaceof the solidat Rn,,");
(iv) constantandequalto D. fiom R,,,",+ 6 to infinity(this
couldrepresent the
electronbeing removedfrom the solid"but with a work functionenergycost of D",
and moving fieely in the vacuumabovethe surfaceand the ad-laver).Sucha
potentialis shorvnin Fis. 2. I 8.
One-
d i m e n s i o n apl o t e n t i a l
s h o w i n ga w e l l ,a
R.r* Rn,u"+ d b a r r i e ra, n d t h e
ElectronpositioncoordinateR + asymptoticregion.
74 M o d e l p r o b l e m st h a t f o r m i m p o r t a n t
s t a r t i n gp o i n t s
The pieceu'isenatureof this potentiarallows

the one-dinre'sionar Schrridi'ger
e q u a t r o n t o b e s o l v e d a n a l y t i cFaol lrye.n e r g i e s
l y i n g i n t h e r a n gD
e" < E < D"
6[', an especiall,r, interesting *
classof sorutions exrsts.Trieseso_cailed
srares resonance
occurat energies thataredete''ined by thecondition
thatthearrpritudeof
thewavefunctionwithinthebarrier(i.e.,for'0:
R < R,,,,,,)belarge.Letusno
turn our attentionto this specificenerg-v
,.gi,r',..i.i,hichalsoser\,,es to introcruce
the tunnelingplrenomenon.
The piecervise sorutionsto the Schrridinger equationappropriate to the reso_
nancecaseareeasirywrittendoil'nin
termsof sinand.o, or.*pon.ntiarfunctro's,
usingthe followingthreedefinitions:
k':\E;c-D\v,r. , -
r' : 11 + SI._ g117;.
2nr"(D"
( 2 . 7 )8
The c.mbinationsof sin(rtR)and
cos(AR)that sorvethe Schrcidin-eer
tn the innerregionand that vanish equario.
at R : 0 (because the functionntustvanlsh
u i t h i n t h er e g i o nw h c r e/ ' i s i . f i n i r e
a n db c c a u s lcr n l u s rb e e o n r i n u o u s .
r''anish at R : 0) is ir musr
W:..1 sin(/,R) (for0< R S Rn,"*).

(2.79t
BetweenR'r^ and Rnr"^* 6. there
are two sorutionsthat obey trreSchrodinger
equation'so the mostgeneralsorution
is a combinationof thesetwo:
W : B n e x p ( r ' R*)B exp(_r,R) ( f o r R n ,<
o .R < R n , u , + d ) . (2.g0)
Finally.in theregionbeyondR,ro"
* d,wecanusea combination of eithers in(k,R)
and cos(fr'R)or exp(ii'R) and exp(-i
t'R) to expressrhe sorurion.Unlike
regionnearR : 0. whereit u as most the
convenient to usetrresin andcosfunctrons
becauseoneof therncould be "thrown
away"sinceit courdnot meet
c o n d i t i o n o f v a n i s h i n g a t R : 0 , i n t h i s l a r y e - R r e g r o n , e r t h e r s ethe
t i sboundary
acceptable.w
chooseto usetheexp(i/,'R) andexp(-i
t"i,, setbe.auseeachofthesefunctrons
an eigenfunction rs
of the momentumoperator-ih,-
/a R.This alrorvsus to discuss
amplitudesfor electronsmo'ing
with positive momentum and with
momentum.So. in this region,the negative
most generalsolutionis
V : Cexp(ll'R)+ Dexp(_if,R) (forR,o+
, 6 < R < cc).
(2.81)
Therearefour amplitudes(A, B+
^ ,8-, andC) thatcanbe expressed in terms
of the specifiedamplitude D of the
incoming iu^ 1..g., pretendthat
the flux of electronsthat our we know
experimentalulpuru,r, ..shoots,,
Four equationsthat can be used at the surface).
io achievethis goarresult when
arematchedat Rmuând at R-u* v and dv/d^
* 6 (oneof the essentiar propertiesof solutions
to the Schrcidinger equationis that they and their flrst
derivativeare continuous;
thesepropertiesrelareto V
beinga profabilitf un._, rU
1U Obeinga momentum
Electron
tunneling 75
operator).Thesefour equationsare
.4 sin(tR.".) : B-. exp(r'Rn'u.)* B exp(-r'R,',,*), ( 2 . 8)2
It cos(l'R"','): t<'B* exp(r'R..,) - rc'B- exp(-r'R.o*) ( 2 . 8 )3
B - e x p ( r ' ( R , n "+- t ) ) + B - e x p ( - r ' ( R , u * * 6 ) )

: C e x p ( r t ' ( R n , ,*r 3 ) + D e x p ( - i t ' ( R n , o** 3 ) , (2.84)
r ' B - e x p ( r ' ( R . u * 6 ) ) - r ' B - e x p ( - r ' ( R , n " ,+ 6 ) )

= ik'C exp(ik'(Rn,"* * 3)l - ik D exp(-i /r'(R",",* 6)). (2.85)
It is especiallyinstructiveto considerthe valueof A I D thatresultsfrom solving

this set of four equationsin four unknownsbecausethe modulus of this ratio
providesinfbrmation about the relative amount of amplitudethat exists inside
the barrier in the attractiveregion of the potentialcomparedto that existing in
the asymptotic region as incoming flux.
The result of solving for .4I D is
* 3 )] {exp(r'3 )(ik' - r')[r' sin([ Rn,,,,

A I D : ;lr,,'exp[-1,{'(R,,,,,, )
+ I c o s ( , ( R , , , " .i)k)'l + e x p ( - l r ' l i ) ( i t ' + r ' ) [ r ' s i r r ( R
l ,,,,)
- I cos(/r/?,,,,,, ' ( 2 . 8)6
))l i k' | .
Further.it is instructil'eto considerthis resultunderconditionsof a high (lar-ee

D. * d L' - E\ and thick (larged) barrier.In sucha case.the "tunnelingfau^tor"
exp(-r'd) lvill be i,'erysmallcomparedto its counterpartexp(k'6).and so
ik'r'
' 1I D : 1 - - L
-
e r p [ - i ( ' 1 R , , '+. , ') ) ]c x p -( r ' 6 ) [ r ' s i n ( k R , ' 1
".
tA r'
'
+ ,( cos{{'R,,,.,,
)l t 1 . 8r7
The exp(-r'd) factorin A I D causesthe magnitudeof the rvavefunctioninside

the barrierto be small in nrostcircumstances; we say that incidentflur must
tunnelthroughthe barrierto reachthe innerregionand thatexp(-r'd) -eives the
p r o b a b i l i toyf 't h i st u n n e l i n u .
Keepin rnindthat. in the energvrangewe are considering(E < D" * d), a
classicalparticlecould not evenenterthe region R,n".{ R . R,..* f d; this is
why we call thistheclassically forbiddenor tunnelingregion.A classicalparticle
startingin the large-Rresioncan not enter.let alonepenetrate. this region,so
sucha particlecouldneverendup in tlie 0 < R < R,.,,,innerregion.Likewise.a
classical particlethatbeginsin the innerregioncanneverpenetrate thetunneling
regionandescapeinto the large-Rregion.Wereit not for the factthat electrons
obeya Schrodinger equationratherthan Newtoniandynamics.tunnelingwould
not occurand for example.scanningtunnelingmicroscop;- (STM), ll'hich has
provento be a wonderfuland pow'erfultool for imaging moleculeson and near
76 M o d e lp r o b l e m st h a t f o r m i m p o r t a n ts t a r t i n g
points
surfaces. wourdnot exist.Likewise,manyof the

devicesthatappearin our mod_
ern electronictoolsand which dependon currentsinducecr
-qalxes, by tunneiing
throughvarious-iunctions, wourdnot be availabre.But. rf .;;;;;.,rn*
occurand it can haveremarkableeffects. oo.,
trt. ur examinean especia,yimportant(in
. chemrstry,)phe'omenonthattakes
placebecauseof tunneringand that
occurswhen the energyE assumesvery
values.The magnirudeof the A/D
:p:cial factorin the abovesorutionsol.the
Schrcidinger equationcan becontela.g. ifth. energy
C is suchthat
r srn(A'Rn,r,)
* A cos(kR,,,.*
) C . 8 8)
r s s r n a l lI.n f a c t .i f
t a n ( { ' R , r , r: " ) - k l r '

(2.89)
thedenominatorfactorin AID will vanish andA/D will
becomeinfinite.lt can
be shownthattheaboveconditionis similar
to the energyquantization
condition
tan(lR,n,*): -k/r
(2.e0)
that ariseswhen boundstatesof a finite
potentiarwe, are examined.There
hou'ever.a difference.In thebound-state is,
situation,rwo energy-reratecr
paranreters
occur
k: \EpE/tt ( 2 . e) r
and
,:rEu1o"-syy; (2.92)
In the casewe are now considering,fr
is the same.but
( : . 9 3)
ratherthanr occurs,so the two tan(frR.u")
equationsare not identical,but they
are quite similar.
Anotherobservationthat is usefurto
makeaboutthe sifuationsin whichA
becomesvery largecanbe madeby considering /D
thecaseofa very high barrier(so
that r' is much larger thank).In this
case,the lenominator that appearsin
A /D.
_R' m a x
r' sin(tR."^)* I cos(lR.u*): r, sin(rtR,u,),
Electron coordinate R
_ (2.e4)
canbecomesmallif
One-
m e n s r o n apl o t e n t i a l
s i m i l a rt o t h e t u n n e l i n o sin(tR-u,,;:9.
(2.es)
pote.ntialbut without
t-he This conditionis nothing but the
oarrrerand asymptotic energyquantizationconditionthat occurs
the particle-in-a-box for
region. potentialshown. nig. z.re. This
potentiaris identicalto
the potentiarthat we were examining
for 0 5 R < Rma*,but extendsto infinitv
E l e c t r o nt u n n e l i n q
beyondR,n,,, ; thebarrierandthe dissociationasymptotedisplayedby our potential

areabsent.
Let's consider'"vhatthis tunneling problem has taught us. First, it showed
us rhatquantumparticlespenetrateinto classicallyforbiddenregions.It showed
that.at certainso-calledresonance tunnelingis muchmorelikelythanat
energies,
"off resonance".In our modelproblem,
ener-sries thanare this meansthat electrons
impingingon thesurfacewith resonance energieswiil havea very high probability
of tunnelingto producean electronthat is trappedin the 0 < R < Rn,o"resion.
By the wav. we could have solved the four equationsfor the amplitude C
of the outgoing wave in the R ) R.o* region in terms of the I amplitude.We
might want to take this approachif wantedto model an experimentin which the
electronbeganin the0 < R . R,,,".regionandwe wantedto computetherelative
amplitudefbr the electronto escape.However,if we were to solve for C lA and
then examineunder what conditionsthe amplitudeof this ratio w'ouidbecome
small (so the electroncan not escape),we would find the sametan(ftRma,):
-k f rc' resonance conditionaswe fbund from the otherpoint of view This means
that the resonance energiestell us fbr what collision energiesthe electronrvill
tunnel inward and producea trappedelectronand, at these same energies,an
electronthat is trappedwill not escapequickly.
Wheneverone has a barrier on a potentialenergysurface.at energiesabove
the dissociation asymptotcD. but belowthe top of the barrier(D. + ,l y' here),
onecan expectresonance statesto occurat "special"scatteringenergiesE. As
we illustratedrvith the model problem,theseso-calledresonance energiescan
oftenbe approxirnated by the bound-state energies ofa potentialthat is identical
to the potentialof interestin the innerregion(0 < R < R',"*)but that exlends
to infinitybeyondthe top of the barrier(i.e.,beyondthe barrier.it doesnot fall
b a c kt o r a l t r e sb e l o u E ) .
The chemicalsignificance of resonances is great.Highly rotationallyexcited
moleculesrray ha'"'emore thanenor.rgh total energyto dissociate(D"). but this
energymaybe"stored"in therotationalmotion.andthevibrationalenergymaybe
lessthanD.. In termsof the abovemodel.high angularmomentummayproduce
a significantcentrifugalbarrierin the effectivepotentialthat characterizes the
molecule'svibration,but the system'svibrationalenergymay lie significantly
below D.. In sucha case.and when viewedin termsof motion on an angular-
momentum-modified efi'ectivepotentialsuchas I showin Fig. 2.20.the lifetime
of themoleculewith respectto dissociation is determined by therateof tunneling
throughthe barrier.
In that case,one speaksof "rotationalpredissociation" of the molecule.The
Iifetimer canbeestimated by computingthefiequencyu at whichflux thatexists
insideRrr* strikesthe barrierat R,,,,,,,
t1K
y = _ (s ,) (2.e6)
2trR,",,,
78 M o d e l p r o b l e m st h a t f o r m i m p o r t a n ts t a r t i n g
potnts
Melrstcblc rotJtronal le\ el
rG) + h?[Ju +
Radial
potentialfor
l'(R) for non-rolatingmolecule
n o n - r o t a t i n g( J : 0 )
motecule and for
rotating molecule.
and thenmultiplyingby the probability p

rhatffux tunnelsthroughthe barrier
fronr R.", to R,rr^* d:
P = exp(-2r'3) (2.e7)
The resultis that
t l N
f = --- c' "\ F
n /t - ) , , '' ^t r u l
) " P | InlSr
-ts
(2.e8 )
u'ith the energy f entering into fr
and r' being determinedby the resonance
c o n d i t i o n(:r ' s i ' ( t r R - o ' ) * r c o s ( r R - , " ) ):
m i n i m u m .e y l o o t i n g b a c ka t t h e
defintionof r', we note that the probability
of tunneringfalrs off exponentia'y
with a factor dependingon the rvidth d
of the barrier throughwhich the particre
must tunnelmultipliedby r,, which depends
on the heightof the barrierD" 3
abovethe energy .E available.This exponential *
dependenceon thicknessand
height of the barriersis somethingyou
should keep in mind becauseit appears
i n a l l t u n n e l i n gr a t ee x p r e s s i o n s .
Another importantcasein u,hich tunnering
occursis in erectronicailymera_
stablestatesof anions.In so-calredshap..einunce
srares,,n.-r"t""i',,.ô",,
electronexperiences:
(i) anattractivepotentiar
dueto its interaction
with theunderlying neutralmorecure,s
dipole.quadrupole. andinducedelectrostaticmoments, aswellas
(ii) a centrifugarpotentialof.theformL(L + r)h2
/gn r,"R2 *hos. .agnitude
depends on theangurar characterofthe orbitaltheextraerectron occupies.
when co'rbined.the aboveattractive
and centrifugarpotentialsproducean
tive radial potentiarof the-form shown efrec_
in Fig.2..2rfbr the 1y'f casein which
addedelectronoccupiesthe n* orbital the
whii has z - 2 characterwhen vieu,ed
E l e c t r o nt u n n e l i n g
Effective
r a d i a lp o t e n t i aflo r t h e
excesselectronin N!
o c c u p y i n gt h e z * o r b i t a l
w h i c hh a sa d o m i n a n t
L = 2 component,
L ( L + 1 l l ] / 8 n 2m # .
from the centerof the N-N bond.Again. tunnelingthroughthe barrierin this

potentialdetennine.s the lif-etimes
of suchshaperesonance states.
Althoughthe examplestreatedaboveinvolvedpiecewiseconstantpotentials
(so the Schrridinger equationand the boundarymatchingconditionscould be
solved exactly),many of the characteristicsobservedcarry overto morechenti-
callyrealisticsitr.rations.
In fact.onecanoftenmodelchemicalreactionprocesses
in termsof motionalonga "reactioncoordinate"(.r)froma regioncharacreristic
of reactantmaterialsr''utere the potentialsurfaceis positivelycurvedin all direc-
tion and all forces(i.e..gradientsofthe potentialalongall internalcoordrnates)
vanish.to a transitionstateat r.vhichthe potentialsurface's cllrvaturealon-q.r'
is R e g i o no f
a c t iV a t c d
negatir,e while all othercurvaturcsarepositir'eand all forcesvanish:onw'ardto
corrplex
productmaterialsrvhereagainail curvatures are positiveand all forcesvanish. Reactants
A prototypicultracc of the encrgyvariationalong such a reactioncoordinate
is sho'uvnin Fig.2.22.Near the transitionsratcat the top of the barrieron this Energy
surface.tunnelingthroughthe barrierplaysan importantrole.if the massesof ile along a reaction
p a t hs h o w i n gt h e b a r r i e r
the particlesmoving in this regionare sufficientlylight. Specifically. if H or D t h r o u g hw h i c ht u n n e l i n g
atomsare involvedin the bondbreakingandformin_e in this regionof the cncrgy m a y o c c u r .
surface. tunnelingmustusuallybe considered in treatingthe dynamics.
Withinthe above"rcactionpath"pointof view..motiontransvcrse to the reac-
tion coordinate.i is clftenniodeledin termsof local harmonicmotionalthough
moresophisticated treatmcntsof the dynamicsare possible.This pictureleads
one to considermotion along a singlc degreeof freedom(s), with respectto
tvhichnruchof the abovetreatmentcan be carriedover.coupledto transverse
motionalongall otherinternaldegreesof freedomtakingplaceunderan enrirely
positivelycurvedpotential(which thereforeproducesrestoringfclrcesto mole-
mentaw'ayfrom the "streambed"tracedout by the reactionpaths ). This point of
view constitutes oneof the mostwidelyusedanclsuccessful modelsof molecular
reactlondynamicsand is treatedin moredetailin Chapter8 of this text.
2 . 7 A n g u l a rm o m e n t u m
2 . 7 . 1O r b i t a a
l n g u l a rm o m e n t u m
A particlenro'ing rvith momentump at a positrclnr relative
to sonrecoordr-
nateorigin has so-calledorbital angularmomentumequal
to L : r x p. The
threeconrponents of this angularmomentumvectorin a cartesiancoordinate
systemlocatedat the origin rnentioned
abovearegivenin termsof the cartesian
coordinatesof r and p as follo,,vs:
L-=tp,.-tJt,. ( 1 . 9)9
L, : . t ' l t .- : 1 t , . ( 2 .I 0 0 )
L,.::p, * xlt,.
( 2 l. 0 l 1
using the fundanrentar
commutationrerationsarlong the cartesiancoordi-
natesandthe Cartesian
momenta:
[ q t . p i l : 4 t p r - p i 4 t = i h 6 /1 i . t = , r . r , . : ) .
tl.l0lr
rt canbe shownthatthe abo'e angularmomentum
operators
obeythe folro$,ing
s e lo f c o m m r r t a t i or n
elations:
[ 2 , .Z , ] - i t t L . . ( 2 r. 0 3)
lL,.L.l: itlL,. (2.r0.1)
lL,.L,l: ihL,. (2.105)
Although the cornponentsof L do rot comnlutewith
one another.they can be
shoivnto commutewith the operatorZ2 definedby
L) : L: + Li + L:. (2.106)
This new operatoris referredto as the squareof the
total angularmomentum
operator.
The conmutation propertiesof the components
of L allow us to conclude
that completesetsof functionscan be founcithat are
eigenfunctionsof Z2 and of
one, but not more than one, componentof L. It is convention
to selectthis one
componentas 2., and to label the resultingsimultaneous
eigenstates of L2 and
L, as ll. n) accordingto the correspondingeigenvalues:
L2lt.nt):hlt(t+l)ll.n), /=0. 1.2.3.....

(2.107)
L , l l . n ): l a n l l , m ) , m : * t , * ( / - t ) .+ ( t _ 2 ) . . . . t ( t _ ( / _
I)).0
( 2 .r 0 8 )
Theseeigenfunctionsof L2 andof z, will not, in
general,be eigenfunctionsof
eitherz' or of 2... This meansthat any measurement
of z, or 2.,.wilr necessariry
changethe uave function if it beginsas an eigenfunction
of 2,.
The aboveexpressionsfor Z._,L,, andL, canbe
mappedinto quantumrne_
chanicaloperatorsby substitutingx,
v-, and z as the correspondingcoordinate
A n g u l a rm o m e n t u m 81
operatorsand-i/10 l0x . - ihd ldt,, and -ihd l0z for p.,. p,,, andp_-.respectively.
The resultingoperatorscan then be transformedinto sphericalcoordinatesthe
resultsof which are
L, = -uto/tte. ( 2 .l 0 e )
L . : i t t l s i n Qi ) l A e+ c o r 0c o s gd l i ) Q | . ( 2 .l l 0 )
L , : -i fi{cos d AlAe - cot0 singdl0Ql. (2.1 I t)
L 2 : - t 1 : { ( l /s i n 6 )d / a d ( s i n d l a 0 +
) ( l / s i n :0 ) d 2l , ) O 2 l ( 2 . rl 2 )
2 . 7 . 2P r o p e r t i e so f g e n e r a la n g u l a rm o m e n t a
There are nlany types of angular momentathat one encountersin chemrsrry.
orbital angularmomenta.snchasintroduced above,arisein electronicmotionin
atorrs.ln atom-atomand electron-atom collisions,and in rotationalmotion in
molecules. Intrinsicspinangularmomentumis presentin electrons. Hl , H2,cl3.
andmanyothernuclei.In this section,we will dealwith the behaviorof anvand
all an_qular momentaandtheircorresponding eigenfunctions.
At times.an atom or moleculecontainsmore than one type of angularmo-
mentum.The Hamiltonian's interaction potentialspresentin a particularspecles
may or may not causetheseindividualangularmomentato be coupledto an
appreciable extent(i.e..the Harniltonianmay or may not containtermsthat re-
t'ersimultancously to two or moreof theseangularmomenta).For example.the
NH- ion. lvhichhasa rf[ grouncielectronicstate(its electronicconfigurarion is
1 s i , 2 o l 3 o r 2 p ; , : p l ,) h a se l e c t r o n iscp i n .e l e c t r o n iocr b i t a l a. n dm o l e c u l arro r a -
tionalangularmomenta.The full HamiltonianH containstermsthat couplethe
electronicspin and orbitalangularmomenta.therebycausingthem individuallv
to not commutervith H.
In suchcases.the eigenstates of the systemcan be labeledrigorouslyonly
by angularmomenturnquanrumnumbersj andn belongingto the totalangular
momentumJ. The totalangularmomentumof a collectionof individualangular
momentais defined.component-by-component. as follows:
"l '. -- \ - t - Itli). ( 2 . I13 )
where,tlabels.y.-r,,and:, andl labelsthe constituents

whoseangularmomenra
coupleto produceJ.
For the remainderof this section.we will study eigenfunction-eigenvalue
relationshipsthat are characteristic
of all angularmomentaanclwhich are con-
sequences of the commutationrelationsarxongthe angularmomentumvector's
threecomponents. we will alsostudyhow one combineseigenfunctions of two
or moreangularmomenta{J(i )} to produceeigenfunctions of the total J.
82 Modelproblems
thatform important
startingpoints
Consequencesof the commutation relations

Any setofthreeoperators
thatobey
[J,. J,] - ittJ,. (2.1t1)

14. .I.l : ittJ,. (2.1 l-5)
[J-.J,l : irlJ,. ( 2 r. l 6 )
will be takento definean angularmomentunt
J. whosesquareL) : Ji + Ji + .l;
commuteswith all three of its components.It is useful to also introducetwo
combir.rationsof the threefundamentaloperators:
J*:.1, tiJ., Q.lt7)

and to refer to them as raising and lowering operatorsfor reasonsthat r,r,illbe
made clear below. These ne\\' operatorscan be shown to obel, the follorving
commutationrelations:
l J 2 .J - l = o . ( 2 . 1l 8 )
1.1.. Jxl - tTtJ+. (2.1l9)
Usingonly theabovecommutation properties,it is possibleto proveirnportant

propertiesof theei-cenfunctionsandeigenvalues of J2 andJ.. Let us assumethat
lvehavefounda setofsimultaneous eigenfunctions ofJ2 andJ.: thefactthatthese
two operatorscol.nnrute
tells us thatthis is possible.Let us labelthe eigenvalues
belongingto thesefunctions;
J . l 1 . m 7: n ' . f t i . m ) l j . n t ) . (2.120)
J . l j . n t )- h n l j . n ) . ( 2 . 1I2)
in termsof the quantities
rl andJ'(j . m). Althoughwe cer.tainly "hint"
thatthese
quantitiesmust be relatedto certainj andnt quantumnumbers.we havenot yet
proventhis, althoughwe will soondo so.For now.rvevieu' ./'(.1. m) andrir simpll,
as symbolsthat representthe respectiveeigenvalues. Becauseboth J2 and J, are
Hermitian,eigenfunctions belongingto different.f ( j. m) or r? quantumnumbers
must be orthogonal:
( i . n t I j . m ' ) = 3 , , , . , , ., , 5 (2.122)
we now prove severalidentitiesthat are neededto discoverthe inforrnatron
about the eigenvaluesand eigenfunctionsof generalangularmoment3that we
are after.Later in this section,the essentialresultsare summarized.
(i) There is a maximum and a minimum eigenvaluefor ,I,

Becauseall of the componentsof J areHermitian,andbecausethe scalarproduct
of any function with itself is positivesemi-definite,the following identity holds:
( j . n t l J i + L l . t . i . m l : \ J , ( . j , m l J , u . m+) ( J , \ j , n r l J , ) j . n )> 0 . (2.t23)

A n g u l a rm o m e n t u m 83
-
Ho*,ever.Ll + li is equalto J2 -/-2,so this inequalityimplies that
( j . m l J ) - l i l i . m ) = / r 2 1 1 ' 1nit.1- m 2 l > 0 . (2.1211)
nhich. in turn, implies that nt2 must be lessthan or equalto -f(j.lz). Hence,
for any value of the total angularmomentum eigenvalue/, the ;-projection
eigenvalue(rr) must havea maximum and a minimum value and both of these
mustbe lessthan or equalto the total angularmomentumsquaredeigenr,aiue ,/'.
(ii) The raising and lowering operators changethe "I. eigenvaluebut not
the ,I2 eigenvaluewhen acting on 17.rl)
Applyingthe commutationrelationsobeyedby Ja to 17.z ) yields anotheruseful
result:
J , J " l j . n ) - f i J , l j . m ) : I l 1 1 o11. . 7 , (2.t2s)

J 2 J L l j . m -) J * J ) l i . n t ) - 0 . (2.126)
Now,usingthe fact that 17.n) is an eigenstate

of J2 and of -/,, theseidentities
give
J . J - \ j . n ) : 1 p 7+ l i ) J = l j . n l = l d m + l ) l j , n ) . (2.t27)
Jt Jt .l .n) : r11
.11i.nJ J-) j. m'1. ( 2 .r 2 8 )
Theseequationsprovethat the functionsJalj. m) must either themselves be

e i g e n f u n c t i o n s o f - / r a n c i - / . , w i t l i e i g e n v a1l u1e. 1.sm
n2) a n d h ( m- t l ) o r J + l j . m )
mustequalzero.In the formercase.we seethat I actingon Ij, n) generates
a new eisenstatewith the srme Jr eigenvalue as lj. m) but with one unit of fi
higheror lolver in -/, eigenvalue.It is for this reasonthat we call .,/* raisingand
lorveringoperators. Noticethat,althoughJalj. m) is indeedan eigenfunction of
. r . w i t h e i g e n r , a l u( em t l ) l i . J + lj . i r r ) i s n o t i d e n t i c atlo l j . m t 1 ) ; i t i s o n l y
proportionalto l/. r? + l):
J - l i . m ) : C 7 , , , l jn. t J : 1 ) . ( 1 .I 2 9 )
Explicitexpressions fbr theseCf,,,coefficients will beobtainedbelow.Noticealso

that becausethe -/- 17.rr ) , and hence17.m X. 1), havethe same-I2 eigenvalueas
17.n) (in fact.sequential applicationof -Q canbe usedto showthat all lj, m'),
for all nr'. havethis sameJ2 eigenvalue). the -/2 eigenvaluef(j.n) must be
tndependent ofrr. For this reason,./ canbe labeledby one quantumnumber7.
(iii) The ./2 eigenvaluesare related to the maximum and minimum ,I-
eigenvalues which are relatedto one another
Earlier,we shor.vedthat thereexistsa maximumand a minimum value for n. for
any glven total angularmomentum.It is when one reachestheselimiting cases
that J-l.i . m) : 0 applies.In particular,
J * l ..jn t ^ ^ ) : 0 . (2.r30)
J-l j. ntî,) = Q. ( 2r. 3 1
)
Applying the following identities:
J J. - J2 - J: -hJ,. (2.132)
J+J : J2 - J.2+h.1,, ( 2 .r 3 3 )
respectively.to 1.7,z-u*) and 17.nln ln) gives
r / l . f j . r r - a " ) - r r l o *- n r * o , ]: 0 . (2.134)
h1l.f U. /??min) - zrfl,n+ rr,ln = o. ( 2 . 31 5)
)
which imrnediately givesthe J2 eigenvalues
f(7. n.r^) and.f (.j. ntni) in terms
of r?n,u*or mmin'.
f (.j. m^^,): nl.u*(riro^ * I ). ( 2 .I 3 6 )

. l (j , m ^ , " ) : r l r n , ; n ( n l n-, ; nl ) (2.1
37)
So, u'e now know the -I2 eigenvalues for lj,m,no*)and 1.7.
rr?min).However,we
earliershowedthat 17.rr) and lj.m - 1) havethe same_/l eigenvalue (u,henwe
treatedthe effectof I on l.l,nr)) and that the J2 eigenvalueis independent
of
m. If we thereforedefinethe quantumnumber7 to be tnmar,we seethat the J:
eigenvalues aregivenb1
J 2 l i . m ) : t 1 2j ( j * t ) 1 1 , m 1 . (2.r38)
We also see that
-f(j,,n): j ( j * 1 ) : m ^ u * ( m ^ u+* 1 ) : n . ; n ( r l n , ; -n l ) , (2.13e)
from which it follows that
lzlmrn: -l/lmax.
(2.r40)
(iv) The j quantum number can be integer or half-integer

The fact that the z-values run from j to - j in unit steps(becauseof the properry
ofthe -! operators)meansthat thereclearlycan be only integeror half-integer
valuesfor 7. In the former case,the rfi quantumnumber runs over -j, -j +
l , - j + 2 , . . . , - j + ( j - 1 ) ,0 , 1 ,r , . . . , j t i n t h el a t r e r , , r ?
u n so v e r- 7 . - 7 *
l , - j + 2 . . . . , - j + ( i - l l 2 ) , 1 1 2 , 3 1 2 , . . . , 7 .O n l yi n t e g ear n dh a l f - r n r e g e r
valuescan range from j to -j in stepsof unity. Specieswith integerspin are
known as bosonsand thosewith half-integerspin are calledfermions.
A n g u l a rm o m e n t u m AR
(v) Moreon J+lj.m)

Usingthe aboveresultsfor the effect of -[ actingon Ij. m) and the fact that -/*
andJ- areadjointsof one anothel allows us to write:
( j . m l J - J * l j . n ) : | i . * l ( J ' - J : - h J , )U , m l
= t l 2 U U* t ) - m ( m* t ) ]
: l J + U ,m l J l l j , r y ) : ( C i ) 2 , ( 2 . 111)
whereCl.u,is the proportionalityconstantbetweenJ+U , m) and the normalized

functionIj , m + 1). Likewise,the effect of -I- can be expressedas
( j . m J a l _ l j , m )= q i , ^ l ( J . - J : + h J , ) t j . m )
: h 2 l i( i * t ) - m ( n - 1 ) |
: ( J _ ( j .m l J l j . m ) : ( C 1 . ) 1 , (2.t42)
whereC,..,,is the proportionalityconstantbefweenJ_l j, m) and the normalized

l i . m- t ) .
Thus,we can solve for C1.,,after which the effectof -/a on Ij . m) ts given by
J - l j . n t ) : t t l j ( j* l ) - m ( m + l ) ) ' / ? l m
/.t1l. (2.113)
2 . 7 . 3S u m m a r y
The aboveresultsapply to any angularmomentumoperators.The essentialfind-
ingscanbe summarized as follows:
(i) J) andJ. ha'e complete setsof simultaneous

eigenfunctions.
we labelthese
eigenfunctionsj. n): theyareorthonormalin boththeirm- and i -typeindices:
U , m j ' . n ' ) : 3 , , , .5, ,.,, .
(ii) These17,rr) eigenfunctions obey
Jtli..) :htjtj + I)li.m). / : integerorhalf-integer (2.1,14)

J.lj.ntl:tttnlj,m), , n = - j , i n s t e p s o fI t o * 7 . (2.145)
(iii) The raisingand lowerin-eoperators.-/+act on lj. m) to yield functionsrhat are
eigentunctionsof ./: with the sameeigenvaluesas Ij , m) and eigenfunctionsof -/,
with eigenvaluesof (rr * l)ft:
J . tj . n 1 : l t l j t j + l t - m t m * l ) l r r . i . m = l l . 1) lJ6 |
(tv) When Ja actson the "extremal"states17,j) or

lj, -7), respectively,the resultis
zero.
The resultsgiven aboveare,as stated,general.Any and all angularmomenta
havequantummechanicaloperatorsthat obey theseequations.it is conventionto
designatespecifickinds ofangular momentaby specificletters;however,it should
be kept in mind that no matterwhat lettersare used.thereare operators
correspondingto J2, J,, and I that obey relationsas specifiedabove,and there
do Model problems that form important starting points
are eigenfunctionsand eigenvalues that haveall ofthe propertiesobrainedabove.

For electronicor collisionalorbitalangularmomenta,it is commonto usel.l and
l.: for electronspin,S: and S, areused;for nuclearspin 1: and I aremost
corltlolt: and for molecularrotationalangularmontentum.N: and ,\; are ntost
common (althoughsontetimesJ2 and.t, nravbe used1.Whencvertwo or more
angularmomentaarecombinedor coupledto producea "total" angular
monrentum. the latteris desicnated
bi Jr and J .
2 . 7 . 4C o u p l i n go f a n g u l a rm o m e n t a
If the Hamiltonianunderstudy containstermsthat coupletwo or ntore angu-
lar momentaJ(i ), then only the componentsof the total angularmomentum
J : L J(i ) and J2 will commurewith f1. It is thereforeessenrialto label the
quantumstatesof the systen,by the eigenvaluesof J- and J: and to coltstruct
variationaltrial or model wavefunctionsthat are eigenfunctionsof thesetotal
angularmomentumoperators.The problemof angularmolrentum coupling has
to do with how to combineeigenfunctions of the uncoupledangularmomen-
tum operators,which are given as simple productsof the eigenfunctionsof the
individualangularmotnentafl;l.ii, m1).to form eigenfunctionsof J2 and J..
Eigenfunctions of J,
Becausethe individualelementsof J are formedadditively,but J: is not. ir is
straightforwardto form eigenstates
of
1.:lJJit; (2.t4'7)
i
simpleproductsof the form fft Ij i , nti) areeigenfunctionsof I
r . n t i n t ): l r , ( t ) f ]t . i i , m=i))* , * f l tr,.,,,). (2.148)
and have J, eigenvaluesequal to the sum ofthe individual ntpll eigenvalues.

Hence,to form an eigenfunctionwith specifiedJ andM eigenvalues, one must
conrbineonly thoseproductstatesll, lji,nti) whosen;fi sum is equalto the
specifiedM value.
Eigenfunctions of J2: the Ctebsch-Gordon series

The taskis thenreducedto forming eigenfunctions
lJ. M),given particularvalues
for the {jr } quantumnumbers.When couplingpairs of angularmomentall.i , m)
and lj', rr')), the total angularmomentumstatescan be written, accordingto
what we determinedabove.as
lJ,M) = lcl I,,,,,li. m)lj',nt'), (2.149)

#r
i,:
:.t A n g u l a rm o m e n t u m 6t
wherethe coefficientsCl.j!,i ., are calledvector coupling coefficients(because

angularmomenfumcoupling is viewed much like adding two vectorsj and j'
to produceanothervectorJ), and wherethe sum overm andm' is restrictedto
rhos!-terms for which ffi * m' : L'l. lt is more common to expressthe vector
couplingor so-called Clebsch-Gordon (CG) coefficients
as (j . m; j' . ni I J. II)
view them as elements of a "matrix"
and to whose columns are labeledby the
coupled-state-/. M quantum numbers and whose rows are labeled by thequantum
characterizing the uncoupled "product j'
numbers basis"7, m; ,m .It turnsout
thatthis matrix can be shownto be unitary so that the CG coefficientsobey
j ' , n l I J . t t 4 l . ( j . mj ';. m ' I J ' . M ' ) : d L . L , | u . , v , (2.I s0)

l{l.,r,
and
\-l ; -. ;' n' I r ,r.t\ j',m' ( 2 . 1 5) 1

/J\r\,.,J t\j.m: I J, ill)- :3u.,,6,,.,,,
This unitarity of the cG coefficientmatrix allows the inverseof the relation

giving coupledfunctionsin terms of the productfunctions:
(2.152)
to be r.vrittenas
l i . m l l j ' . n i ) : L U . n t :j ' . m ' I J M ) " ) J . M )
:
f t t . t 4 t ,i . m ; j ' m ' ) l J . I t ) . ( 2r.s 3 )
Thisresultexpresses
the productfunctionsin termsof the coupledangularmo-
mentumfunctions.
Generation of the CG coefficients

The CG coefficientscan be generatedin a systematicmanner;howeverthey can
alsobe lookedup in bookswherethey havebeentabulated(e.g.,seeTable2.rl
of R. N. Zare..lngulur illomentunr.John Wiley, New York (1988)).Here,we
will demonstrate the techniqueby rvhichthe CG coe{fcientscan be obtained.
but we rvill do so lor ratherlimited casesand refer the readerto more extensir,e
tabulations.
The strategywe take is to generatethe lJ, J) srate(i.e., the statewith ma.xi-
mum M-value) and to then use -/_ to generatelJ. J - l), after which the state
l./ - l. -r - l) (i.e.,the statewith one lower-/-value)is constructed by findinga
combination of theproductstatesin termsof which lJ, J - l) is expressed (be-
c a u s e b o tl hJ , J - 1 ) a n dl - r - l , J - l ) h a v e t h e s a mM e - v a l u eM : J -ll
w h i c hi s o r t h o g o n at ol l J . J - l ) ( b e c a u sleJ - 1 . . / - l ) a n d l J , - / - l ) a r e
eigenfunctions of the HermitianoperatorJr corresponding to differentergen-

values.they must be orthogonal).This sameprocessis then usedto generate
l J . J - 2 ) l J - 1 . J - 2 | 1 a n d ( b y o r t h o g o n a l i tcyo n s t r u c t i o nl )J - 2 . J - 2 ) .
and so on.
(i) The stateswith maximum and minimum M-values

We begin with the statel-I../) havingthe highestM-r'alue.This statemust be
formedby takingthe highestlz andthe highestrr' values(i.e..m : j andnt' :
7'). and is givenby
(2.5
14)
Only this one product is neededbecauseonly the one term with rt - .7 tnd
m' : i'contributesto the sum in the aboveCG series.The state
I r ,- r ) : t i ,- . i | j ' . - j ' ) ( 2 .s15)

with theminimum M-vaiue is alsogivenasa singleproductstate.Noticethatthese
stateshaveM-valuesgivenas +U + /'): sincethis is the maximumM-value,it
must be that the J-value correspondingto this stateis J : j t .i' .
(ii) Stateswith one lower M-r,alue but the same "/-value

Applying J- to I.I. J), and expressingJ- as the sum of lowering operatorsfor
the two individual ansularmomenta:
J_:J_(t)+J,(2) ( 2 .l 5 6 )
gives
J - l J . h : 1 1 1 J ( J+ l ) - J ( J - I ) ) r i r l " r . " l/ )-
: ( J - ( l ) + r - ( 2 ) ) l j ,i ) l i ' j ' )
= h u u + 1 )- j u - l ) ) ' / , | j , - 1 | j " j ' )+ n 1 1 ' 1a. 1 '1
_ j , l j ,_ t ) | , / r U
j t .U , j. , _ r ) . (2.157)
This result expresseslJ, J - l) as follows:
l J . J - 1 ) : [ { , r ( ,+i 1 ) - j ( j - l ) } ' / ' l J j, - t ) l i ' . i ' )

+ I . i ' U+' t ) - i ' ( i ' - 1 ) ] ' / 2i|)i U
, ' ,i ' - 1 ) l
lJ(J + t) - J(J - l)1-rr:. (2.i58)
that is, the IJ, J - I ) state,which hasM : -/ - l, is formedfrom thetwo product

states17,j - lllj' ,7') and lj, j)l j' , j' - 1) thathavethis same M-value.
(iii) Stateswith one lower "I-value

To find the state lJ -1,J -l) that has the same M-value as the one found
abovebut one lower ,/-value,we must constructanothercombinationof the two
p r o d u c t s t a t e s w iMt h: J - I ( i . e . , l j ,j - l ) l j ' , j ' l a n d l j . j ) l j ' . j ' - 1 ) ) t h a t
A n g u l a rm o m e n t u m
89
is orthogonalto the combinationrepresenting

fJ, J _ t):after doing so,we must
function so it is properry
io.ruri,.a.';;;;r;;r;,
;;;::,ff,:.r"lting the desired
It
r
: t J _ t . J _ t ) : t u u + 1 )_ j ( j _
1)),/21 j )ju. , , j , _ t )
- ti'(j' + t) - j'(j, -
t ) ) t / 2 Uj , _ 1 ) U ,j., ) l
I J ( J + 1 )_ J ( J _ t y _ t r z .
(2.159)
It is straightforwardro showthat this
function is indeedorthogonal
to lJ, J _ t).
(iv) Stateswith evenone lower

,/_yalue
Har-ingexpressedlJ, J _ l) and _
:::a'Jil;l;;'we
1. J
are
no* lJ
o"oo*J'1ryi:'ffi;[
fi."iJ;l;]
combinati ons",*.; :::T:,',' _i ;,1,
l;,L :trt_-rlifr: ir.";,r.,ji il
U ,j - 2 ) U ' , j ' ) . I i , i ) t j , . . j , _ 2 ) , a n d t j . j _ 1 ) U , .
j,_
;
arepreciselyas many product "r,
l). Noticetharthere
stateswhose * ,r, values
M-varueas there are totar angular add up to the desired
momentumstatesthat must
(therearethreeofeach in be constructed
this case).
stepsneededro find thestat; -
l-l 2, J -2) areanarogous ro thosetaken
.rJ::
( r ) o n e f i r s r a p p l i e st.o, /l_- r _
l . - r _ l ) a n dt o l J , J _ l ) r o o b r a i n
and1,./ . ./ _ 2). respectively; l J _ 1 .J _
os.ombinotion,,) r l i ' i - 2 ) t i ' ' i ' ) ' U ' i ) U2")i ' - 2 ) .
ti,i- tlti'.i'-,,.
(rr) Onethenconsrructs _
tJ 2. J _ 2) asa linear
ti.i)ti'.i' - 2),aw)
tj.j _t)ti,
./,_r)*"::,1?il:::illny.j,,;,-lli;J,,
fbundfortJ_t._
J2)and
tJ.J_2).
once l-r - 2, J - 2) is
obtained.it is then possibre
lJ,J-3),tJ-I.J-3), to move on to form
r1d lt_z,j_:,1by a p p l y i n -g/ _ t o t h e t h r e e
tnpreceding
apptication
;:::yiTi
-,,| "i::n,,1";U',11;i,;ilJ##
I
ortn. p.o..r,lonJ,o
thenrbrm
.i, tj
:: :)li;
obtarne f,*:ll,;;l*j
f odr l J , J - 3 ) . t J _ I , J _ 3 ) , a n d
Againnoticethatther tt _Z.J _3).
rn; ;;'; ;. ;; ""ffi: TH'.'jt'nc orrec
h.r.r"u, t numberorproduct states(rour
states
andrherotal ""*",- momentum r,"r;,;.'.o
:q"u?in.*l#il,j::?:TJ,;
f i"'J::iTH:l#::::r:nsets
d;;; ;' (i t'''tii,"i c;,;;:i,,.,",
1l1nitary;bec-,",,,""0T*Xiliiil?,i,?;I|J"'Jllff
setscontainingthe ::"."T,n:Tffi
:i;
samenumberof functions.
An example
Let us consideran examplein r.l,hich the spinandorbitalansularmomentaof the
Si atomin its 3Pgroundstatecanbe coupledto producevariousrp.7states.In tl.ris
case,the specificvaluesfor j andj' are.f - "!: I and : L: 1. We could-
.i'
o f c o u r s e . t a k e-. Tl : I a n d . l ' : S : l . b u t t h e f i n aul , a y e f u n c t i o n s o b t a r n e
would spanthe samespaceas thosew.eareaboufto determine.
Thestatewith highestM-valueis the-rp(,/|1s : 1. M t : I ) state.u,hichcanbe
represented by the productof an ncvspin function(representing S : i . M s : 1)
anda 3p13p6spatialfunction(represenring L : l. M t : l), u,heretheIirstfunc-
tlon corresponds to the first open-shellorbitaland the secondfunctionto the
secondopen-shellorbital.Thus. the maximurr M-value is M:2 and corrc-
spondsto a stater"'ith -/ : 2:
lJ :2. 1 4: l) : 1 2 .l \ : d d 3 p . . 1 p , , . ( 2 .l 6 0 )
Clearly.the state12.-2) would be given as bt'J3p_t3po.

The states12,l) and 11.l) u'ith one lowerll{-valueareobtainedby applying
J - : S * I L _ t o i 2 . 2 ) a sf o l l o w s :
J 1 2 . 2 :) f r { 2 ( 3- ) 2 ( l) } r / : 1 2l ).
: ( S -+ l _ _ ) a c r 3 p 1 3 p o . (2.161)
To apply s* or l- to oa 3p13ps.one mustrealizethat eachof theseoperators
is. in turn,a sum ofloweringoperatorsfor eachofthe two open-shellelectrons:
S-: S (l)+S-(2). (2.t62)

L_-L_(t)+L (2). (2.r63)
The resultabovecan thereforebe continuedas
( S - * Z - ) a a 3 p r 3 p:o l i l l l 2 ( 3 1 2 ) - | l 2 ( - 1 1 : ) l 1 t 2p a 3 p , 3 p s
+ t f t / 2 ( 3 1 2-) | / 2 ( - 1 / 2 i l t i 2 u p 3 p l p s
* hll (2) - I (0)|r1:oo3pn3p6
+ h l l ( 2 )- 0 ( - I ) l r / r a a 3 p3rp - , . (2.t64)
So,the function12.l) is givenby (ao3p63psviolatesthe pauli principle.so it is
removed)
12.1) : [do3n'3Ru
* uB3p13p()
r {2}tt2ua3py3o_l
/2. ( 2 r. 6 5 )
which can be rewrittenas
12.l) : l(fla + uB;lpr3po+ l2]tt2os3p'3p_,)

/2. (2.166)
writing the result in this way makesit clear that
12,l) is a combinationof the
p r o d u cst t a t e sl , s: 1 , M s : 0 ) l Z : l , M t : l ) ( t h et e r m sc o n t a i n i n e
ls: l.
A n g u l a rm o m e n t u m
91
. t / 5= 0 ) : 2 - t i 2 1 a B + F a ) ) a n dl s : 1 , l v l s : l ) l Z : l . l u l t : 0 ) ( t h et e r m s
g : 1 . f u5l : 1 1 - a . ' ) .
c o n t a i n i nl S
T o f o r m t h e o t h e r f u n c t i own i t h M : 1 ,t h e i 1 , l ) s t a t e , w e m u s t f i n d a n o t h e r
o f
c o r n b i n a t i o nl S : 1 .M 5 : 0 ) l I : l , M 1 : 1 ) a n < ll S : l , M 5 : 1 7 1 7 :
l.,l[L :0) that is orthogonal to 12.l) and is normalized.Since
1 2r. ) : 2 - ' ' t l l s: t . i n s : 0 ) i r : t . M 1 - t ) + l " t : l . , r / . r : l )

x lI = l,Mt:0)),
e.167)
we immediatelyseethat the requisitefunction is
l l . l ) : 2 - ' ' : [ l S - I , M r = 0 ) l Z: t . M L : l ) - l S = l , , V s : t )
x lI = l, illr:97)1. (2.r68)
In thespin-orbitalnotationusedabove.this stateis
l l , l ) = f { f l " + " B 1 l p , 3 p-u { 2 } , ' 2 a a 3 p } p - 1 )2 . ( 2 r.6 9 )

f
T h u sf a r ,w e h a v ef b u n d t h e3 p . 7s t a t ew
s i t hJ : 2 , M : 2 : J : 2 . ilt: l: and
l - l i . t - l
T o f i n d t h e 3 Psl r a t e s w i tJh : 2 , M : 0 : J : l . M : 0 ; a n d - I :
0.M : 0.
we must once agarnapply the -/_ tool. In particular,u,e applv,/_
to 12.l) to
o b t a i n1 2 . 0 )a n d u , ea p p l y- / _ t o l l . l ) t o o b t a i n
l l . 0 ) , e a c ho f w h i c h w i l l b e
e x p r e s s ei ndt e r m so f l . S : l . M 5 : 0 ) l l : l . M 1 ,: 0 ) .
l.t : l. M.;: l)lt :
l . i l [ 1 : - l ) . a n dl S : I . M 5 - _ l ) l L : l . M 1 : i ) . T h e
1 0 . 0 )s t a t ei s t h e n
constructed to be a combinationof thesesameproductstateswhich is orthosonal
t o 1 2 . 0 )a n dt o l l . 0 ) . T h e r e s u l t sa r ea s f o l l o w s :
) . J : 2 .t r : 0 ) : 6 " . 1 2 1 l . 0 ) l t . 0I l) .+l ) l l ._ l ) + I i . _ l ) l t . r ) 1 .( 2 . r 7 0 )
l J : r . , v : 0 ) : 2 - , , , | 1 .l ) l l ._ l ) _ l l . _ l ) l l . l ) 1 .
Q.t7t)
l . J: 0 . , V : 0 ) : 3 , , [ l r . 0 ) l t . 0 ) _ l ll ). l l . _ l )_ l t . _ t ) l l ,1 ) 1 . ( 2 . 1 7 2 )
where. in all cases.a shorthandnotation has
been used in which the
l-t. ,I'l.s)|L . llt L) productsstatedhavebeenrepresented by their quantumnumbers
with the spin function arrvaysappearingfirst in the product.
To finally express
all threeof thesenervfunctionsin termsof spin-orbitalproducts
it is necessary
to gi'e the l.l. rvy) lL . l,l t.) procluctswith M : 0 in terms
of theseproducts.For
thespin functions,we have
lS: l. Ms = l) = ao. (2.173)

l S : I , M s - 0 ) = 2 - t t 2 ( c t +p p a ) ( 2 . 117)
s -l) : ff .
l S : I , r l . 1= (2.t1s)
For the orbital product function, we have
It : i. Mt = I):3pr3p,,. (2.176)
JZ M o d e lp r o b l e m st h a t f o r m i m p o r t a n ts t a r t i n gp o i n t s
iZ : l . A 4 r : g y = 2 1 , ' : ( 3 p t , 3* p3op ; 3 p , 1 . (2.177)

lL:1,Mt=-l) :3po3p_i. (2.178\
Coupling angular momenta of equivalent electrons

If equivalentangularmomentaare coupled(e.g."to couplethe orbital
angular
momentaof a p2 or d3 configuration), one mustusethe follorving.,box'.method
to determinewhich of the term symbols'iolate the pauli principle.To carry
out
this step.one forms all possibleunique(determinental)
productstateswitli non-
negativeM 1 andM5 valuesand arrangesthen.rinto groupsaccordingto
rheirM 7,
and M5 r'alues.For example.the boxesappropriateto the p: orbital occupancy
are shownbelow:
M v 2
M, I lptcttpoctl Iprap.-ral
U lppptlll l p t a p o f l . l p n a p t f l l p ' c l p _ t f l l . l pr a p r f J ll.p o c r p o f J l
There is no need to form the correspondin-qstates r.l,ithnegative M1,

ornegative
Ms values because they are simply "mirror images" of those listed
above. For
e x a m p l e ,t h e s t a t e w i t h M 1 : -l and Ms: -l is
l p _ r f j p o f J l .w h i c h c a n b e
o b t a i n e df r o m t h e M L : I. Ms: I s t a t e l p l n p e a l b y r e p l a c i n go b y p a n d
replacingpr by p_r.
Given the box entries, one can identify those term symbols that arise
by appry-
ing the following procedure over and over until all entries have
been accounted
for:
(i) one identifiesthe highestM5 value (this givesa varueof the total spin quantum
numberthat arises,s) in the box. For the aboveexample.the answeris :
s l.
(ii) For all productstatesof /?,.rM5 value,one identifiesthe
highestM7_value(this
givesa valueof the total orbital angularmomentum,Z, that can arisey'rr
llrs .f).
Forthe aboveexample,the highestM7 withinthe M5 = I statesis M :
t | (not
ML :2), henceI : l.
(iii) Knowing an ,s, Z combination, one knows the first term
symbol that arisesfrom
this configuration.In the p2 example,this is ip.
(iv) Becausethe level with thesez and s quantumnumbers
conrains(2L + 1x2s + l)
stateswith M1 and M5 quantum numbers running from _Z to Z and from _.!
to
.1,respectively, one must removefrom the originarbox this numberof product
states.To do so, one simply erasesfrom the box one entry u,ith eachsuch
ML and
M5 value.Actually,sincethe box needonly show thoseentrieswith non-necatrve
M7 andM5 values,only theseentriesneedbe explicitly deleted.In the 3p
example,this amountsto deletingnine productstateswith ML, Ms values
of
I , l ; 1 , 0 ;l , - l ; 0 , 1 ; 0 , 0 ; 0-,t ; _ 1 . 1 ;_ 1 , 0 ; _ 1 . _ 1 .
(v) After deletingtheseentries,one returnsto
step 1 and carriesout the processagaln.
Forthe p2 example,the box after deretingthe first nine productstates
rooksas
Angular momentum VJ
follo*'s (thosethat appearin italics shouldbe viervedas alreadycancelledin

countingall ofthe lP states):
,llt 2
,!1, I lpraprpl lptap-pl

0 lpraprdl lpspofJl.lpnap'dl lpsp;Fl,lp-roprEl, lpoapodl
It shouldbe emphasizedthat the processof deleting or crossingoff entriesin

variousML, lvls boxes involves only counting how many statesthere are; by
no meansdo we identify the particularL . S, M t. M5 wave functionswhen we
crossout any particularentry in a box. For example,when the lprcvpodlprod-
uct is deletedfrom the Mt: I. r!1s:0 box in accountingfor the statesin
3P level. we do not claim that lP
the lpgpofrl itselfis a memberof the level;the
lpocvp rf I productstatecould just as well be eliminatedwhen accountingfor the
lP states.
Returningto the p2 exampleat hand.after the lP term symbol'sstateshave
beenaccountedfor, the highestM5 valueis 0 (hencethereis an ^S: 0 state),and
within this Me value,the highestII 1,valueis 2 (hencethereis an L :2 state).
T h i s m e a n st h e r ei s a r D l e v e lr , v i t hf i v e s t a t e sh a v i n gM t : 2 . 1 . 0 . -1. -2.
Deletingfive appropriateentriesfiom the abovebox (again denotingdeletions
by italics)leavesthe followingbox:
,llt 2
M, l Ip l a p x u l lptap tul
U lpsptlJl l : r a p r t l J l . ' , p r u p r f l lp t u p r f 1 . \ p _ t a p t f l l . l p , r a p o f l
The only r:mainingentry,which thus has the highestM5 and M1 values.has

t/s : 0 andM y : 0. Thusthereis alsoa lS levelin the p2 configuration.
T h u s ,u n l i k et h en o n - e q u i v a l e2npt r 3 p i c a s e i,n w h i c hl B ' P ,l D , ' D , 3 S , a n d
lS levelsarise.
only the lP. lD. andls arisein the p2 situation.It is necessary
to carry out this "box method" wheneverone is dealingwith equivalentangular
momenta.
If one has mixed equivalentand non-equivalent angularmomenta,one can
determineall possibtecouplingsof the equivalentangularmomentausingthis
methodandthenusethesimplervectorcoupling methodto addthenon-equivalent
angularmomentato each of thesecoupledangularmomenta.For example.the
p:dl configurationcan be handledby vectorcoupling(usingthe straightforwarcl
non-equivalent procedure) Z : 2 (thed orbital)and,S: I l2 (thethird electron's
spin)ro eachof 3p,rD,and iS. The resultis .F, .D, .p, 2R 2D,,q ,G, 2F.2D,2p
2 S .a n d2 D .
2.8 Rotationsof molecules

2 . 8 . 1R o t a t i o n aml o t i o nf o r r i g i dd i a t o m i ca n d l i n e a r
p o l y a t o m i cm o l e c u l e s
This schrodinger equation relatesto the rotation of diatomic and linear
polyatomic molecules.lt also ariseswhen treating the angular motions
of electronsin any sphericallysymmetric potential.
A diatomicmoleculervith fixedbond lengthR rotatingin tlreabsenccof any

externalpotentialis describedby the followingSchrodinger
equation:
-h'l I a (ri,,r1')--f-!-)r:ur
( 2 . 17 9 )
2/t LR: s"*/ rl', \ r J H/ R- sin- F i)Qt )
t : ,'t ,
-- 'F' ,"t ', (2.180)
2lLR:
wherez- is the squareof the total angularrnomentumoperatort,? + tl

+ tl
expressed in polarcoordinates
above.The anglesd and@describetheorientatlon
of the diatornicmolecule'saxis relativeto a laboratory-fixed
coordinatesysrem.
andpr is the reducedmassof the diatomicmoleculeU : il.t1ttt2f(mr * ri:). The
differentialoperatorscan be seento be exactlythe sameas those that arosern
the hydrogen-likeatom caseas discussedabove.Therefore,the samespherical
harmonicsthat servedas the angularpartsofthe wavefunction in the hvdrogen-
atomcasenow serveasthe entirewavefunctionfor the so-calledrigid rotor: :
v/
YL.u@.@).Theseare exactlythe samefunctionsas we plottedearlierwhen we
graphedthes (Z : 0), p (L : 1),andd (L : 2) orbitals.Theenergl,eigenvalues
correspondingto eachsucheigenfunctionare given as
_ h2JtJ+ll
tL: :BJ\J-ll (2.181)
zttn,
andareindependentof M. Thus eachenergylevelis labeledby J andis (2J + 1)-
foid degenerate (becauseM rangesfrom -J to -r). Again, this is just like we saw
when we lookedat the hydrogenorbitals;the p orbitalsarethree-folddegenerate
and the d orbitals are five-fold degenerate.The so-calledrotational consranr
B (definedas tl2121t"R21 dependson the molecule'sbond length and reduced
mass.Spacingsbetweensuccessive rotationallevels(which are of spectroscopic
relevancebecause,as shown in chapter 5, angularmomentum selectionrules
often restrictthe changesLJ ]n J that can occurupon photonabsorptionto 1,0,
and -l) are given by
LE : 311+ 1X-/+ 2)- BJ(J* 1): 2p11* t, (2.182)

Theseenergy spacingsare ofrelevance to microwavespectroscopywhich probes
the rotationalenergylevelsof molecules.In fact,microwavespectroscopy
offers
R o t a t i o n so f m o l e c u l e s 95
themostdirectway to determinemolecularrotationalconstantsandhencemolec-
ularbondlengths.
The rigid rotor providesthe most commonly employedapproximationto the
rotationalenergiesand wave functionsof linearmolecules.As presentedabove,
themodelrestrictsthebond lengthto be fixed.vibrational motion of the molecule
givesrise to changesin R which are then reflectedin changesin the rotational
energylevels.The couplingbetweenrotationaland vibrationalmotion givesrise
to rotationalB constantsthat dependon vibrational stateas well as dynamical
couplings.calledcentrifu-eal distortions,thatcausethe total ro-vibrationalenergy
of the moleculeto dependon rotationaland vibrationalquantumnumbersin a
non-separable manner.
"rigid rotor"
Within this model, the absorptionspectrumof a rigid diatomic
moleculeshoulddisplaya seriesofpeaks.eachofwhich corresponds to a specific
J - J f I transition.The energiesat which these peaks occur should grow
linearlywith -r. An exampleof such a progressionof rotationallines is shown
inFig.2.23. The energiesat which the rotationaltransitionsoccurappearto fit
the AE:28(J * l) formula ratherwell. The intensitiesof transitionsfrom
level-/ to level -/ + 1 \,ary stronglywith J primarily becausethe populationof
moleculesin the absorbinglevel varieswith -/. Thesepopulationspr are given.
whenthe systemis at equilibrium at temperaturer, in terms of the degeneracy
(2J + 1)of the-/th levelandtheenergyof thislevelB J(J + l ) by theBoltzmann
formula:
p . r: e - t e J * t ) e x p ( - 8 , / ( , 1+ 1 ) l k T ) (2.r83)
wherep is the rotationalpartition function:
O =ltzL * l ) e x p ( - B - r (+J t ) l k T ) (2.18.1)
For low valuesof -/, the degeneracyis low and the exp(-B-r(J +l)l kr)
factor is near unity. As -/ increases,the degeracygrows linearly but the
Typical
rotationalabsorption
profileshowing
intensityvs. J valueof
the absorbinglevel.
exp(- B J ( J + 1) I k T ) factor decreases more rapidly.As a result,thereis a value

o f J , g i v e nb y t a k i n gt h e d e r i v a t i v oe f ( 2 J - l 1 ) e x p ( - B J ( J + 1 ) l k T ) u ' i t h r e -
spectto J and settingit equalto zero.
2 J - u ^* l : 1 , 5 f f i . (2.1g5)
at which the intensityofthe rotationaltransitionis expectedto reachits maxrmurn.

This behavioris clearly displayedin the abovefigure.
Theeigenfunctions belongingto theseenergylevelsarethesphericalharmon-
ics Yt.v@, @)which arenormalizedaccordingto
u,@.0)sin0dedQT:3tt,6r.u'. (2.186)
As notedabove,thesefunctionsare identicalto thosethat appearin the solu-

tion of the angularpart of hydrogen-likeatoms.The aboveenergl' levels and
eigenfunctions also apply to the rotationof rigid linearpolyatomicmolecules;
the only differenceis that the moment of inertia / enteringinto the rotatior.ral
energyexpression is givenby
I:lm,R; ( 2 r. 8 7 )
wherenr,,is the n.rass

of theath atomand Ro is its distancefrom the centerof mass
of the molecule.This momentof inertiareplacespR2 in the earlierrotational
energylevelexpressions.
2 . 8 . 2R o t a t i o n am
l o t i o n so f r i g i d n o n - l i n e a m
r olecules
Therotationalkineticenergy
The rotationalkinetic energyoperatorfor a rigid polyatomicmoleculeis
H,o,: Jj /2t" + J: l2tb + J: /2t,., (2.188)
where the lp(k: a,b.c) are the three principal momentsof inertia of the
molecule(the eigenvaluesof the moment of inertia tensor).This tensorhas el-
ementsin a Cartesiancoordinatesystem(K,K' : X,Y. Z), whoseorigin is
locatedat the centerof massof the molecule,that can be computedas
/r.": I m , ( n ' -, n ' r . ) (forK: K') ( 2 . 81 e )
Ir.r,: -LmiR*tRr,.i g o rK I K'). (2.190)
As discussedin more detail in Chapter6, the componentsof the quanturnme-

chanicalangularmomentumoperatorsalong the threeprincipal axesare
J"- -ttcos
x(*,rr\ - ##) - iisinx (2.r9r)
$
R o t a t i o n so f m o l e c u l e s 97
(."tea-
Jt= ittsinx
# il. ihco'xfi (2.1e21
,
Jc:
- a
-lll:-
( 2 .r 9 3 )
dx
The angles0 . Q, and x are the Euler anglesneededto specify the orientationof
the rigid moleculerelativeto a laboratory-fixedcoordinatesystem.The corre-
spondingsquareof the total angularmomentumoperatorJ2 canbe obtainedas
J2:Jj+t]+Lj
a2 1 /a2
: - ' d 0 : ,- c o t^?a- * *
a2-
2cos0 =
6: \
t2'1941
,i,r, \ro, ax: ).
and the componentalong the lab-fixedZ-axis J7 is -ili\lD6 as we saw much
earlierin this text.
The eigenfunctions and eigenvalues for specialcases

(i) Sphericaltops
when the threeprincipal momentof inertiavaluesare identical.the moleculeis
termeda sphericaltop. In this case,the total rotationalenergycan be expressed
in termsof the total angularmomentumoperatorJ2
H , , ,= J ) l 2 [ . (2.19s)
As a restrlt.the eigenfunctionsof Hro,are those of J2 and Ju as well as J7,
both of which commute with J2 and,with one another.,,/7 is the component
of J alongthe lab-fixedZ-axis and commuteswith Jo becauseJz: -ihAlAQ
and J,, - -iliD/Dx act on different angles.The energiesassociatedwith such
eigenfunctions are
E(J. K. M):h2J(J + I)/2t2 (2.t96\

for all K (i.e., Jn quantumnumbers)rangingfrom --l to -/ in unit stepsand for
all l,I (i.e., Jz quantumnumbers)rangingfrom -J to -/. Each energy level is
therefore(2.1+ l)2 degenerate becausethereare 2J + I possibleK valuesand
2J + | possibleM valuesfor eachJ.
The eigenfunctionsj-l. M. K) of J2, J7 andJo , aregiven in terms of the set
of so-calledrotationmatricesDt.tr.x..
D I - Ll
, J . 1 4K
. \: D ) v K @ . Q x. t . (2.re7)
v il
which obey
J l ) J . ] , t ,K l : h 2L ( L + l ) l J , M , K ) , (2.r98)
J , , I JM, . K ) : h K l J ,M . K ) , (2.t99)
J z l J .M . K ) : t 1 M l JM
, , Kt. (2.200)
oa M o d e l p r o b l e m st h a t f o r m i m p o r t a n ts t a r t i n gp o i n t s
TheseD.7..v.1'fu'ctions areproportionalto the sphericalhar'ronicsYt.tr().0)

multipliedby exp(iKX)"lr'hichreffectsits X-dependence.
(ii) S1'mmetrictops
Moleculesfor which two of the threeprincipalmomentsof incrtiaareequalare
calledsymrnetrictops.Thosefor which the uniquemomentof jnertiais smaller
than the othertwo aretermedprolatesymmetrictops:if the uniquemomentof
inertiais largerthan the others,the moleculeis an oblatesvrnmetrictop. An
An.rericanfootball is prolate,and a frisbeeis oblate.
Again.tlrerotationalkineticenergy.which is the full rotationalHamilronran"
canbe u'ritten in termsof the total rotationalan_tularmomentunroperatorJl and
the componentof angularmomentumalongthe axis with the uniqueprincipal
n'roment of inertia:
H , o , : . / :l 2 l + J : l l l 2 l " - l l 2 l l f o r p r o l a treo p s . ( 2 . 2 0) 1
Hu, : J2l2l + J,2l l2l, - | l2t I for oblatetops. (2.2021
Here,the momentof inertia ,1denotesthat momentthat is conrmonto trvo direc-

tions;thatis, / is thenon-unique
momentof inertia.As a result.theeigenfunctions
of H,o, are thoseof J: and Ju or J, (and of J7), andthe correspondingenergl,
levelsare
E ( J ,K . M ) = h 2J ( J + j ) 1 2 t 1+ f f 1 2 1pt r , , _ t l 2 t ) (2.2031
for prolatetops,
E ( J .K . M \ : t r 2 J ( J + t ) / 2 r 2+ t t 2 K 2 l t / 2 t-, l l 2 r ) (2.20-+)
for oblate tops. again for K and M (i.e., Jo or J, and J7 quantumnumbers,
respectively)rangin-qfrom -J to J in unit steps.Sincethe energynow depends
on K, these levels are only 2J * 1 degeneratedue to the 2J * 1 different M
valuesthat arise for eachJ value. Notice that for prolate tops, because1., is
smallerthan I, the energiesincreasewith increasingK for given -/. In contrast.
for obiatetops, since ,I..is largerthan 1, the energiesdecreasewith K for given
J. The eigenfunctionslJ. M , K) arethe samerotationmatrix functionsas arise
for the spherical-topcase,so they do not requireany further discussionat this
time.
(iii) Asymmetric tops

The rotationaleigenfunctionsand energylevelsof a moleculefor which all three
principal momentsof inertia are distinct (a so-calledasyrnmetrictop) can not
easily be expressedin terms of the angularmomentumeigenstatesand the J,
M, and K quanfumnumbers.In fact, no one has ever solvedthe corresponding
Schrodingerequationfor this case.However,given the threeprincipal moments
ofinertia Io, I6,and I",amatrixrepresentationofeach ofthe threecontributions
V i b r a t i o n so f m o l e c u l e s qq
to the rotationalHamiltonian
12 r2 12
r.; J' J:
u - '
- ( 2 . 2 0)5
2t, 2tr, 2t.
canbe formedwithin a basissetof the { lJ. M . K)l rotation-matrix
functionsdis-
cussedearlier.This matrixwill not be diagonalbecausethelJ. M . K) functions
are not eigenfunctionsof the asymmetrictop H.o1.However,the matrix can be
formed in this basisand subsequentlybrought to diagonalform by finding its
eigenvectors{Cn..r.v.x}andits eigenvalues {f,,}. The vectorcoefficients
express
the asymmetrictop eigenstates as
v ' @ ' o''' = / a C n' t ' K l JM

' 'K ) ' (2.206)
Becausethe total angular momentum /2 still commuteswith H,o,.each such

rvill containonly one -/-value.and hencev,, can also be labeledby a
eigenstate
./ quantumnumber:
\ U ,. t @Q
. ,X ) : C , ,r \ rK ) J .M . K ) . (2.207)
I
To form theonly non-zeromatrixelementsof H,o,within the lJ. M, K) basis.

one can use the fbllowing propertiesof the rotation-matrixfunctions(see.tbr
example.R. N. Zare.AngularMomennun,JohnWiley.New york (198g)):
( J , M . K i J , i l . t i. l t . K ) : \ J . M . K I J ; . J . M , K )
. V l * J : i J . L r .K )
: t l 2 \ J . , r . tK
:h:[J(,]+l)-K:1. (2 . 2 0)8
(2.209)
( J . , V . K l JJ ,. it t . K + 2 ) = - . ( J . , V . K l J ; l J . M+. 2K1
= h ' 1 . / (+J l ) - K ( K + l ) l r: u ( - /+ l )
- (( + lxK + 2)lr':, (2.210)
(2.2rl)
Eachof theelements of .1 . J,i.andJolmust,of course,bemurtipriedrespectivelv.
by 1121,.| 121,,.and I 12l6 and summedtogetherto form the matrixrepresenra-
ttonof 11,u,.
The diagonalization of this matrixthenprovidesthe asymmetrictop
energlesand rvavefunctions.
2.9 Vibrationsof molecules

T h i s S c h r o d i n g e er q u a t i o nf o r m s t h e b a s i sf o r o u r t h i n k i n ga b o u t b o n d
stretchingand angle bending vibrations as well as collectivevibratioi-rs
calledphonons in solids.
Theradialmotionof a diatomicmoleculein its lorvest(J : 0) rotationallevel

can be describedby the following Schrcidinger
equation:
tl.lllr
l r ' h e r ep i s t h e r e d u c e dm a s sF : m 1 m 2(f n t 1 + m 2 ) o f t h e t w o a t o m s .I f t h e
moleculeis rotating.thenthe aboveSchrodinger equationhasan additionalterm
J ( J + 1 ) h 2 / 2 L L r2 l r o n i t s l e f t - h a n d s i d e . T h u s , e a c h r o r a t i o n a l s t a t e ( l a b e l e
the rotationalquantumnumberJ) hasits own vibrationalSchrodinger equation
and thus its own setof vibrationalenergylevelsand u'avefunctions.It is com-
mon to examinethe J : 0 vibrationalproblemand then to usethe vibrational
levelsof this stateas approximations to the vibrationallevelsof srateswith non-
zero J values(treatingthe vibration-rotationcoupling via perturbationtheorv
introducedin Section4.1).Let us thusfocuson the J : 0 situation.
By substitutinglr : F(r)lr into this equation,one obtainsan equationfor
F(r) in which the differentialoperatorsappearto be lesscomplicated:
li1 d2 F
-i * I/(r\F: EF (1.213)
a,-,
This equationis exactlythe sameas the equationseenearlierin this text for the
radial motion of the electronin the hydrogen-likeatomsexceprthat the reduced
mass/.. replacesthe electronmass/ri and the potentialI/(r) is not the coulomb
potential.
Ifthe vibrationalpotentialis approximatedas a quadraticfunctionofthe bond
displacementx : t' - r. expandedabout the equilibrium bond lengthr. where
Z hasits minimum.
V=1/2k(r-r,)2 (2.214)
the resultingharmonic-oscillatorequationcan be solved exactly.Becausethe

potential Iu grows without bound as x approachesoc or -oo, only bound-state
solutionsexist for this model probiem. That is, the motion is confinedby the
nature of the potential, so no continuum statesexist in which the two aroms
boundtogetherby the potentialare dissociatedinto two separareatoms.
In solvingtheradialdifferentialequationfor thispotenrial,thelarge-rbehavior
is first examined.For larger, the equationreads
#:)r.'(#), (2.2ts)
where x : r - re is the bond displacementaway from equilibrium. Defining

q:gtklh2)t/4x as a new scaledradial coordinateallowsthe solution
of the
large-r equationto be written as
fiu.g.": exp(-(2 l2). (2.2t6)

V i b r a t i o n so f m o l e c u l e s
101
The ge'eral solution to the radial equationis then expressedas this large-r
solutionmultiplied by a powerseriesin the ( variable:
F : :-
- r er v! n \/ -/ . tLl , / / _? t \ \r - n erl-
(2.217)
n=v
wherethe c, are coefficientsto be determined.Substitutingthis expressioninto

the full radial equationgeneratesa set of recursionequationsfor the c,, ampli_
tudes.As in the solutionofthe hydrogen-likeradial equation,the seriesdescribed
by thesecoefficientsis divergentunlessthe energy E happensto equarspecific
values.It is this requirementthat the wavefunction not divergeso it can be nor_
malizedthat vields energyquantization.The energiesof the statesthat anseare
gir en by
E,, : h(.k
/ p)t'2(n + | /b. ( 2 . r28 )
andthe ei-eenfunctions
aregivenin termsof the so-calledHermitepolvnomiars
H,,(v)as lbllows:
t t 2 1 a / ry r r a
Ir,(x) : qn!2") e x p l - a - r : / 2 ) H , ,( u t i ) x ) , ( 2 .r2e )
wherea : (ktrtl/1-1ti2.
within this harmonicapproximation
to the potential.the
vibrationalenergylevelsarc'evenlyspaced:
A E : E , + r - E , : t t , k lp ) t ' 2 (2.220\
In experimental datasuchevenlvspacedener,syIevelpatternsare seldomseen:
most commonll,.one finds spacingSEr*l _ 8,, that decreaseas the quantum
numbern increases. In suchcases.one saysthat the progression of vibrational
l e v e l sd i s p i r ls u n h a r m o n i c i r v .
Because theHermitefunctionsH,,areoddorevenfunctionsof.r (depending
on
whethern is odd or even).thervavefunctionsry',, (-r) areodd or even.This splittin_q
of thesolutionsinto tr'",o distinctclasses is an exampleof theeffectof symmetry;
tn this case.the symmetryis causedby the symmetryof the
harmonicpotential
rvith respecrto reflectionthroughthe origin along the -r-axis(i.e..
chansrn,s .r-
to --r). Throughoutthis text. many symmetriesarise:in
eachcase.symmerry
propertiesofthe potentialcausethe solutionsofthe
Schrtidingerequationto be
decomposed into varioussymmetrygroupings.Suchsymmetrydecompositions
areofgreatusebecause theypror,ideadditionalquantumnumbers(i.e..symmerry
labels)by which the wavetunctionsandenergiescan be labeled.
The basic idea u'derlying how such symmetriessprit the solutions
of the
Schrcidinger equationinto diftbrent classesrelatesto the fact that a symmerrv
operator(e.g..the reflectionplane in the aboveexample)
commuteswith the
Hamiltonian.That is. the symmetryoperatorS obeys
SHq/ : HS:\y. (2.22r)

So -l leavesH uncl.ranged as it actson ff (this ailows us to passs throughff in

the abo'e equation).Any operatorthatreavesthe Hamirtonian
(i.e..the energv)
unchanged is calleda syrnnetrvoperator.
If you ha'e never learnedabout horv point group
symmetry can be usedto
helpsimplifythe solutionof the Schrcidi.ger equation.thiswouidbe a goodtime
to lnterruptyour readingand go to chapter4 andrea<i
the rnaterialthere,
The harmonicoscillatorenergiesand 'u'avefunctions
conrprisethe simprest
reasonable model for 'ibrational nlotion.vibrationsof a polyatomic
molecule
areoftencharacterized in termsof incliridualbo'd-stretchi'ganda'gle_bending
motions.eachof which is. in rurn.approximated ha'.ronicalry.This resurtsin a
total vibrationalwavefunctiontl.ratis writtenas a product
of funcrions" one fbr
eachof the vibrationalcoordinates.
T\l'oof the mostseverelimitationsof the harrnonic
oscillatornrodel,the lack
of anharmonicity(i.e., non-uniforn.r ener-qvrevel spacings)and lack of. bond
dissociation. result from the quadraticnatureof its potenrial.By
introducing
modelpotentialsthatallow for properbonddissociation (i.e..thatcio,ot increase
without boundas,t --r co). the nrajorshortconrings
of the harm'nic oscillator
picturecan be overcome.The so-calledMorsepotentiar
(seeFis.2.24)
I/(r) - D"ll - exp[-a(r -.")]]: (2.222\

is often usedin this regard.
In the Morsepotentialfunction.D" is the bond dissociation
energy,r. is the
equilibriumbond length, and a is a constantthat
the ,.steepness,,
characterizes
of the potentialand thus affectsthe vibrational frequencies.
The advantageof.
usingthe Morsepotentialto improveupon harmonic_oscillator_level
predictions
Morse
potentialenergyas a -6
function of bond length. 2
Internuclear
distance
V i b r a t i o n so f m o l e c u l e s 103
is that its energyler''elsand wave functionsare also knorvnexactly.The energres

aregiven in termsof the parametersof the potentialas follows:
u,=,(x),[ft.;)
(,+ 1)'o(X)'''
4,n
. (2.223)
wherethe forceconstantis givenby k :2D, a2. The Morsepotentialsupporrs

bothboundstates(thoselying belowthedissociationthresholdfor which vibration
is confined by an outer turning point) and continuum stateslying abovethe
dissociationthreshold.Its degreeofanharmonicityis governedby the ratio ofthe
harmonicenergy/1(klp;tlz to the dissociation energyD..
The eigenfunctionsof the harmonicand Morsepotentialsdisplaynodalchar-
acteranalogousto what we haveseenearlierin the particle-in-a-boxmodelprob-
lems.Namely, as the energy of the vibrational state increases,the number of
nodesin the vibrational wave function also increases.The state having vibra-
tional quantumnumberv has v nodes.I hope that by now the studentis getting
usedto seeingthe numberof nodesincreaseas the quanfumnumberand hence
theenergygrows.

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The Basics of Quantum Mechanics: 1.1 Why Quantum Mechanics Is Necessary For Describing Molecular Properties

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C h a p t e r1

The basicsof quantum mechanics

1.1 Why quantum mechanicsis necessaryfor describing

but a nervset of equationscalledSchrodingerequations.when scientistsfirst

where d is the spacingbetweenneighborin,u planesof atomsor ions. These

coveredby the secondphoton (i.e.,the lengthfront pointsA to B to C; is an

where rl. is the massof the eiectronand i is the constantintroducedby Max

where rl is the mass of the scatteredparticle and /r is Planck's consranr

Theobservation thatelectronsandothersmalllight particlesdisplayivave-like

terrnsof the radiusof the orbit:

The energycharacterizingan orbit ofradius r. relatil'eto the 6 : 0 reference

Both this equationandthe analogousBraggequationare illustrationsof what we

and, in turn. for the velocities ofelectrons in these orbits,

Thesetrvo resultsthen allorv one to expressthe sum ofthe k i n e t i c( l r r . r ' : ) a n c l

g : - ! r , , z t r ' 1 t n l1t 2 t1 ' . (1.r0)

Just as in the Bragg diflraction result,rvhich specifiedat what anglesspecial

is emittedrvhenthe atom or ion undergoesa transitionfiom an orbit having

The Bohr formulafbr energylevelsdid not agreeaswell w ith the observedpattern

where r, is its oscillationfrequency.The arnplitude'sspatialdependence

I (,r.0) : A sin(2r:;l).1. (1.1.1)

where.),is the crest-to-crest

)"= Lln. (1.15)

wherec is the speedat which the wavetravels.This speeddependson the com-

This relationshipimplies,for example.that an instrumentstring made of a very

l(.r. r. /) = sinln,:rr I L.,)sin(n,:ry

Hence.the wavesare quantizedin two dimensionsbecausetheir wavelengths

If I is supposedto relateto the motionof a particleof momentump underno

'ti1= -2,,r('* ,,.

Returningto the time-dependence

which, using the first result.suggeststhat

This is a primitiveform of the Schrcidinger

7.' and - , (:-'\ +

Theseconnectionsbetweenphl,sicalproperties(energyf and mornentump)and

"new and improved"

1.2 The Schrodingerequationand its components

Any experimentallymeasurablephysicalquantityF (e.g.,energy.

Suchan operatorwould occurwhen,for example,one

and the correspondingoperatoris

for which the quantttmoperatoris

*'here Z 1e is the chargeon theTthparticle.Notice that in this case,classicaland

in which the X7 arecalledeigenfunctions andthe (scalarnumbers)cv;arecalled

So. we saythat exp(a_r,) is an ei-eenfunctionof d ldy and a is the corresponding

A specialcaseofan operatorcorresponding to a phvsicalll,nreasurable quan-

actof makingthe measurement causes the system'swavefunctionto becomethe

then.when the propertyG is measuredthe wavefunction'Q : Xtrvili remain

F G7i: r.Q7, (1.-1lt

So. nor.vwe scc that (G;1,) itself is an ei-uenfunctionof F havingeigenvalue

GX,: ltix,. (1.:12)

which meansthat X, is also an eigenfunctionof G. This. in turn. meansthat

subsequent measurementof the secondoperatoru'ill producean eigenvalueof

The ti me-depe n dent eq u ati o n

Beforemovingdeeperinto understanding whatquantummechanics "means".

wherev(qi, t.) is the unknownwave function and H is the operatorcorrespond-

F _ s.Ip; l/r\-e -\-2,"'t

- r+- fl pr j* -r-' -r 'ir- \-? Z'Zr'i

massesare denotedrr. and {n,,}, respectively.The correspondingHamiltonian

't7 l-Ai- - 1\- "' - \- Z,e:w

The Hamiltonianin this casecontains/ nowhere.An exampleof a casewhere11

The ti me-i ndepe ndent eq uatio n

lf the Hamiltonianoperator does not containthe time variableexplicitly,

In caseswherethe classicalenergy,and hencethe quantumHamiltonian,

this "ansatz"into the tir.ne-dependent

ifldF(r)ldt: EF(t) (1.54)