Chapter1 PDF

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. containnuclei 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 experimentalfindin-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
scattered
electronsof(reasonably)
fixedkineticenerg)'E from metalliccrvstals.
Theseworkersfoundthatplotsofthenumberofscattered
electrons
asa functionof
"peaks"
scattering
angled displayed
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
-
ot
I VisibleI
*.'{fllllrilt-Irffi
""'-*,,-onllrll
frlllill
Anarvsis
lrrn
Llf
Emission
spectrumof atomic
h y d r o g e nw i t h s o m e
lines repeatedbelow to
illustrate
t h e s e r i e st o
w h i c ht h e y b e l o n g .
Paschen
Brackett
Theobservation
thatelectrons
andothersmalllight particlesdisplayivave-like
r.vas
important
behavior
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
characteristic
values.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 rationalize
suchspectrain 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,e
Coulombforce(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:

E :
C h a r a c t e r i z a t i o no f
small and large stable
orbits of radii 11 and 12
for an electron moving
arouno a nucleus.
I
- r t t . . r -- Z t ' - , r ' :
f
'
'
-l
Z L ' -/ t ' .
1
(1.6)
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 photons.lt u'asbelievedthatphotoner.nission
occurreduficn an electronr.rrovirrr
irr
a largercircularorbit lostenergyandnrovedto a sn.raller
circularorbit.Hor.r'ever.
the Newtoniandynamicsthatproducedthe aboveequationr.vould
allou'orbrtsof
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

as
Coulombpotential(-Ze2 lrl energies
g : - ! r , , z t r ' 1 t n l1t 2 t1 ' .
) '
(1.r0)
Just as in the Bragg diflraction result,rvhich specifiedat what anglesspecial

there are many stableBohr orbits.
high intensitiesoccurredin the scattering,
value
the
integer
of
ir. Those with small n have small
each labeledby a
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
only certain
it is the resultthat only certainorbits are
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
an
t o m sa n d i o n s{ i . e . .H . H e . L i - : . e t c . ) t o
e m i s s i osnp e c t roaf r l l o n e - e l e c t r 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:
R -
I
-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 constructiveintert-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
nrotionsof light and small;lartrclessuchas electronsand nuclei.
the dynan.rical
on the de
We seethat extraconditions(e.g..the Braggconditionor constraints
u'ith
degree
of
agreenrenl
couldbe imposedto achievcsome
Brogiieu'avelength)
Hou'e'u'er,
u'estill arelcft wonderingr.ihattheequations
observation.
experimental
and why the extra
are that can be appliedto properlydescribesuch motior.rs
areneeded.
It turnsoutthata ner.r'kind
of equationbasedon cornbining
conditions
to address
suchissues.
These
u'aveandparticleproperties
neededto be developed
arethe so-calledSchrddinger
equationsto ri'hichwe no\\'tunr our attention.
equationfollou,s
As I saidearlier.no one hasvet shownthat the Schrodi-qer
from somen.rorefundamentaltheory.That is. scientistsdid not dedeductivelir
rive this equatiotr;
theypostulatedit. Sorre ideaof hou'the scientists
o1'thatera
"dreamedup" the Schriidinger
had
thc
equationcan be
by exan-rir.ring tirre and
thatcharacterizes
travelingu,aves.
lt shouldbe noted
spatialdepcndence
so-called
that the peoplervhoworkedon theseproblcmskneu'a greatdcal aboutu'aves
(e.g.,soundw'avesand \\.ater\\'aves)and thc equationsthey obeyed.Moreover.
of quantized
they kneu' that u,avescould sometimesdisplaythe characteristic
(e.9..
u'avelenqths
fundamentals
and overtonesin soundu'a'"'es).
or fi'equencies
They'kneu',for example.that r.r,a'u'es
in one dinrensionthat are constrainedat trvo
points(e.g..a violin stringheld fixed at tu'o ends)undergooscillatorymotjon
fi'equencies
andu'avelengths.
For exan.rple.
in spaceandtime with characteristic
just
violin
the motion of the
string
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
givenby
a sinusoidaldependence
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 $,avelengths
belongingto 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
F u n d a m e n t aaln d f i r s t
overtone notes of a
v i o l i ns t r i n g .
(1.15)
)"= Lln.
sin(hx/LJ
w h e r en : 1 . 2 , 3 . 4 , . . . T h e
equation.reads
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
d2,4(x,t)
Lll-
. d2A
(l\-
(r . l 6 )
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 compositionof the materialfrom which the violin string is made.Using the earlier
for the -r- and t-dependences
of the wave,A(x,t). we find that the
expressions
rvaves frequencyandwavelengtharerelatedby the so-calleddispersionequation:
v : : ( c l n ) :.
(r .r 7 )
c: tv.
(1.18)
or
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 rectaneulartwodimensionalsurfaceof 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
;(/.\- : - l
andusingthe de Brogliehypothesis
X:
,l:.1
-:-p-l
.1.\'-
/22 \r
. l l
\ ,\ ,/
(1.20)
hlp in the aboveequation.one finds

.71.2 \l
, | ,a
tt
(r.21)
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('* ,,.

)'
n
(1.\'-
(1.22)
or, aiternatively.
-(*)'#: uo
r t 1l\
10
Returningto the time-dependence

of l(.r'. /) and using v : Elh. one can also
show that
/ h \ dA
i ( ^ I ' : E i t '
\tlr
dl
(1.24)
which, using the first result.suggeststhat

th
'\=/
1d.4
:,t,
r lt \:J:A
,..
\;/
(1.2s)
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
connections
e,: h/p an<iE : lr,), bothof
which involvethe constanti. producessuggestive
connections
betrveen
,(+)# and
E
(r . 2 6 )
and bet."veen
r
D-
,
anc
1/t1:d:
\ 2:r) dt:
( 1 . 2| 7
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, logicall1,.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 unusual 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
"new and improved"

theory that describeshow
we are ahvayssearchingfor a
smalllightparticlesmove.
If it helpsyou to be more acceptingof quantumtheory,I shouldpoint out
descriptionof particleswill reduceto the classicalNewton
that the quantLrm
undercertaincircumstances.
In particular,when treatingheavypardescription
massesand evenheavieratoms),it is oftenpossibleto
ticles(e.g.,macroscopic
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
equationthat lve havebeendi-eressing
aboutfor so long.
Schrodinger
1.2 The Schrodingerequationand its components

that electronsmoving in atomsand moleculesdo
It hasbeenwell established
not obeytheclassicalNewtonequations
of motion.Peoplelong agotriedto treat
electronicnlotionclassicallv.
and tbundthat featuresobservedclearlyin erperimentalmcasurements
simplywerenotconsistent
with sucha treatment.
Attentpts
r,vere
madeto 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 scientists
realizecl
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.
is castin a languasethat is not farniliarto moststudents
Quanturnrnechanics
of chemistryrvhoare exarrininsthe subjectfbr the first timc-.Its nrathernatical
contentandhorvit relatcsto experimental
measurements
bothrecluire
a -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
equation.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 experimentalrreasurement
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.
t l
12
Any experimentallymeasurablephysicalquantityF (e.g.,energy.

dipole mo_
ment.orbitalangularmomentum.spin angularmomentum,
linearmomentum,
kineticenergy)hasa classical
mechanicar
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 coordinates
97 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/2k( q1- ,tl)

+ t, ( q,- q) ,) l
l t'i /2 u ,,+
The quanturnmechanicaloperatorassociatedwith this
t :,I,
(1.29)
.F is
- +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.)
-/= I ..'\'
and the correspondingoperatoris
t : -t,.,:.Iu
(',* - r',+)
( r. 3 2 )
If one transformsthesecartesiancoordinatesand
deri'ativesinto polar coordi_
nates,the aboveexpressionreducesto
F--iltf
i?'
a
3Qi
( 1. 3 3 )
The r--componentof the dipole moment for

a coilection of 1y'particleshas a
classicalform of
\'p -- ./--
Z1exi,
( r.34)
for which the quantttmoperatoris

F:
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 Cartesiancoordinates.To map a classicalfunction .E,given in termsof curvilinearcoordinates
(evenifthev are orthogonal),into its quantumoperatoris not at all straightforward. The mappingcan alwaysbe done in terrnsof Cartesiancoordinatesafter
which a transtbrmationof the resultingcoordinatesand differentialoperatorsto
a curvilinearsystemcan be performed.
The relationship
of thesequantummechanical
operators
to experimental
measurementlies 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
(coming
F usuallircontainsdifferentialoperators
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-eenfunction
of 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.
12
14
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
quantitv 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
melhodsthatmeasureotherproperties(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:
of a physicalquantityF hasbeencarried
X.i.ln fact,oncea measurement
out and a particulareigenvalue).i hasbeenobserved-the system'srvavefuncrion
v becomesthe eigenfunction1, that correspondsto that eigenvalue.
That is, the
causes
the system'swavefunctionto becomethe
actof makingthe measurement
of
the
property
that tvasmeasured
eigenfunction
What happensif someotherpropertyG, r.vhose
quantummechanicaloperator
is G is measuredin sucha case?We knou' from what was said earlierthar some
pr of the operatorGlvill be observedin the measurement.
ei_genvaltre
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

This propertv.thattheorderofapplicationofthe two operators
unchanged.
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-uenfunction

of F havingeigenvalue
ir. So, unlessthereare l.norethan one eigenfirnctions
of F corresponding
to
the eigenr.aluc
i; (i.c..unlessthis cigenvalue
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,
15
to
subsequent
measurementof the secondoperatoru'ill producean eigenvalueof
that operator.but the systemu'avefunction will be changedto beconrean crgenfunctionofthe 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.
"means".
Beforemovingdeeperinto understanding
whatquantummechanics
it is useful to learn horv the wave functions V are found by applying the basic 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 operatorcorresponding 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
( 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
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
- 1\- "' - \- Z,e:w

l-Ai2n,dq;
??r,,
-tl_ l
a:
'll2n,'dq.;
?,.,"
* 1 l Z , Z n e :\ y
2?
rr.h
;l r!
lnAt
( 1.16)
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
)
Z,rX,,f.cos((r/
)- f
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)
17
18
Substituting
this "ansatz"into the tir.ne-dependent
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,).
ifidF(t)ldt: EF(t).
( l . 5 l)
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
e
x
p
(
i
,
,
i
@
)
:
l
*
f crptiirrd,).
ztra6,1
[:,r,J
ll.-i.l)
In thiscase.rr 2tt2
In thisexample.theHarriltoniancontains
12tvtis theeigenvalue.
the squareof an angularmomentumoperator(recall earlierthat u,'eshou'edtlre
:-cornponent
of angularmomentumis to equal-ih d ldQ).
\Vhen the Schrcidingerequation can be separatedto -seneratea timeindependent
equationdescribingthe spatialcoordinatedependence
ofthe u'ave
function,the ei_eenvalue
E mustbe retumedto the equationdeterminingF(t) to
part of the wavefunction.By solving
find the time-dependent
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
In summary,wheneverthe Hamiltoniandoes not dependon time explicitly,

one can solvethe time-independent
Schrodinger
equationfirst and thenobtain
as exp(-i El/fi) oncethe energyE is known. In the case
rhetime dependence
of rnolecularstructuretheory,it is a quite dauntingtask even to approximately
equationbecauseit is a partialdifferentialequarion
soivethe full Schrodinger
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 applyingquantummechanics to moleculesis knownas the Born-oppenheimer(Bo) approximation.
The
basicideabehindthis approximation
involr.esrealizingthatin the full electronsplus-nucleiHamiltonianoperatorintroducedabove,
H : t l - , iz n tri t'q--: l \ - - " ' - ' t a l

2?'',,
?,,"1
?1
*,-l_fir;rr_l
"
2nr,,;)q,] 2
\..-
7 7 . :
z!/ zxc
';
(r . 5 8 )
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.Thisobservation
motivates
r.rsto solvethe Schrcidinger
equationtbr 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 tit , ": t -, 1*: 1 t ' ' ' - r'Z{

l
t/
)L,".,
I
,,, l'
(1.59)
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.
tv
20
Secondorder saddlePotnl
fransrtion structureA
Minimum for
product A
- 0.,5
Two-dimensional
potentialenergysurface
s h o w i n gl o c a lm i n i m a ,
transitionstatesand
p a t h sc o n n e c t i n g
them.
Secondorder n
saddlepoint
0.5
\ralley-ridgc
i n f l e c t i o np o t n t
Minimum for reactant
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 seetou,ard the end of this introductorymaterial,to geometriesof stablet.nolecular
(labeledtranstructures.The surfacealso displaystwo first order saddlepoints
havezero
points
These
mininra.
sition structuresA and B) that connectthe three
direction
one
have
first derivativeof E.r with respectto both coordinatesbut
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. assumed 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 index 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
statesthatbelongro eachsuchsurface.
lExe,)]) and the vibration-rotarion
Having been introducedto the conceptsof operators,wave functions.the
equation,it is importantto now considerseveral
Hamiltonianandits schrodin-eer
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.vn
in 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
potentials
characteristic
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 .
22
theprobabilitydensitl'.imaginethe particleto havea

To conceptualize
illustrate.
to it andthink of this lampblinkingsay100timesftrreach
blinkinglan.rpattached
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
underNe\\'ton'siau's.
-rRarethe positionsat whichtheparticle,if it weremo'"'ing
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
in the centralplot.
linestouchthe I'(r)plots as sho'uvn
the fractionof'tirllethe
The probabilitydensityat any valueof -r:represents
(i.e..
r/.r).Think of forrrling
u'ithin.r
and,t
value
this
of
..r*
particlespendsat
this density'by allowingthe blinking lantpattachcdto the particleto shedlight
plate that is exposedto tliis light for many oscillationso1on a photo-eraphic
-r1 and;rp. Alternatively.one can expressthis probability
the particlebet\\'een
the spatialdistancer/.r"by thevelocitl'of theparticle
P(r)
by
dividing
amplitude
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

l/ is lou') andri'ill be high
valuesu,heretheparticleis mo'u'ingquickly (i.e..'ui'here
plate
tr/is high). So. the photographic
wherethe particlemovesslowly 1r,r,here
the particlemovesslou'lyin
u'ill shou,a brightregionwhere I/ is high (because
suchregions)and lessbrightnesswhere tr' is lou'.
by analyzingthe
The bottomline is thatthe probabilitydensitiesanticipated
appearasthehistogran.r
classicalNewtoniandynamicsof this oneparticle'uvould
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
slorvly.it spendsmore time and P(.r) is larger.For the plot on the ri_eht,/(,r)
"box".
so the speedis constant.hencep(.r) is constant
is constantwithin the
box. I ask that you keepthesepiots
fLrrall .v valuesrvithinthis one-dimensional
in nrind becausethey are very difrerentfrom what one finds when one solves
equationfor this sameproblem.Also pleasekeepin mind that
the Schrcidinger
represent
plots
what one expectsif the particle were moving accordingto
these
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
lilt
(1.63)
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 probability 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
thisrrreans
thatrheprobabilityof theparticlebeingrt,r
/(-t ) mustbe continuous:
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
^
lnt
dr'
(1.6.+)
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)
23
z4
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 probablyencountered.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.rd
x : 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
t:
l l t t r ) l i , / . t: l . -1t : s i n 2 t r xz I L ) t t x .
J
;l
0.72)
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

\ L
lttl L-/lt
(r.75)
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, andbycharacteristics
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 probability densitieslv(.r)ir that they represent
to 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 .
25
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
Seven
lowestwave functions
andenergies.
Noticethat as the quantumnumbern increases,

the energyE also increases
rvith n in this case)andthe numberof nodesin v also increases.
lquadratically
Also notice that the probability densitiesare very different from what we enearlierfor theclassicalcase.Fo[ example.look at ther : I andil : 2
countered
and comparethem to the classicaldensityillustratedin Fig. 1.10.The
densities
densityis easyto understand
classical
becausewe arefamiliarwith classicaldynamics.In this case,we saythat P(.r) is constantwithin the box because
the fact
rhekineticenergyandhencethe speedofthe particle
that tr/(.r) is constantcauses
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
27
28
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 classicaldynarnicsto 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 variouspositions)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
iI
1 I
11
0.9
0.8
0.7
^.
(\A
5
r!
0.5
V o.c
0.3
0.2
Ouantum
probabilitydensityfor
n : 7 s h o w i n gs e v e n
peaksand six nodes.
I
I
0.1 I
rJ
xlL
I
\
: 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 "
sense
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
with
somewhat
blurred
vision
positions
on
the
and
heights
focusinu
of
1i.e..
very
looks
much
like
the
classical
P(,r)plot
in
which
P(.r)
is
the maxima)
-r.
In
fact,
general
it is a
resultof quantummechanicsthat the
constantfor all
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
Forexample,a givenparticle-in-a-box
energvCn :
dealingwith heavyparticles.
n:h: I \2ntL2) u,ouldbe achievedfor a heavierparticleat highern-valuesthanfor
a lighterpalticle.Hence,heavierparticles,movingwith a givenenergyE. have
higherr and thusmoreclassicalprobabilitydistributions.
thisso-calledquantum-classical
\!'e rvill encounter
principle
correspondence
'nve
again "r,'hen examineother model problems.It is an important property of
equationbecauseit is what allowsus to bridgethe
solutionsto the Schrodinger
"gap" betrveen
usingthe Schrodinger
equationto trearsmall,light particlesand
(big, heavy)systems.
theNewtonequationsfor macroscopic
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
l:
ltrlt,,:,/t:/ .a,,:lt'.
(1.16)
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'
(you haveonly seenone suchcasethus
solutionscontainimaginarycomponents
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
29
5U
not only of theseparticle-inyou r.l'illsoonseethat it is a characteristic

because
from any Schrodinger
obtained
functions
w,ar.,e
a-box wave functionsbut of all
equatlon.
In fact, the orthogonalityproperty is evenbroaderthan the abovediscusston
suggests.It turnsout that all quantummechanicaloperatorsforrnedas discussed
-ihd ldq operator
earlier(replacingCartesianmomentap by the corresponding
to be so-called
shor'vn
can
be
as thev are)
and leat'ingall Cartesiancoordinates
This rneansthat they form Hermitianmatricesu'henthey
Hermitianoperators.
are placed betweenpairs of functionsand the coordinatesare integratedover.
acting on a set of
of an operatorF vu'hen
For example,the rnatrix representation
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

eigenvalues
tl.ratit canbe shownthat suchmatriceshaveall real(i.e.,not cor.t.rpler)
that are orthogonal.
and haveeigenvectors
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
u'avefunctionis
energyEn : n2r2h2lQmLz),the time-dependent
v(x.
r): (?)"',inff*r(-?),
(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
states.For example,considera particlemovingalong
suchstatessuperposition
within the "box" potentialbut in a statewhosewave function at some
the-r--axis
initialtime/:0is
/ 1 7 r \
, / l \ l :
u(ror:,,,(;)'''(
. . r 2 t l :
/ l - z . r ' \
. )-,,(;),'"(?)
{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
: I ;,'",(?) +/ sin:
r,r,r'
(?) - r(?)
|
' t ' n /(
lrr\
/ 1 . - r .tr I
(1.87)
r /t'"( . ,/i
Then : I andn : 2 components,

the superposition
V. andthe probabilityden:
sityat 1 0l V lr areshownin thefirstthreepanelsof Fig. l. 12. It shouldbe noted
that the probabilitydensityassociared
with this superposition
srateis not symmetricaboutthe"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 /:
v ( ;rr1 *: ' ( - # )
['
{,
",'"
' { i ) ' , , " ( T ) - ' ' '(?r)
(?)l
' ( ; )" ' ' ( ? ) ' - io) (- -' '
,'G)"'
"',"(?).-'(-+)]
(r.88)
The spatialprobabilitydensityassociatedwith this W is
,)r::
j{(;),'",(+)
. (;),,'',(?)
rv(r
-'(?).o, - u,)if,',
(+),'"(?)] o8e)
[ru,
5Z
I
d
/ i I
E t,.o
l i . . -
.^
_0.1
>
{)l
u.l
r I--r\
o.E
/f
--
0 ^
lt
!_t
06
f_'
.l
0.i
/ l
(1.-l
()l
0
( 1I.
-t
t
I
\
!
-0:
X,L
04
1.6
{
t:
^l
t.l
f
.\
t:
0 N
-1^
{
\
6l
I
\
0.6
.=
:
i.
1).1
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 particle 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
.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.
wavefunctionscan offer"to someextent,the opportunityto tbllow
superposition
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"
the particle'smovements.but only to the
In a sense.this allor.vsus to
are
that'"ve
satisfied
with
ascribingits locationto the positionof the major
extent
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 theoretical chemistrycommunityaimedat developingelicient approximations
to the
exp(-i t H lll) evolutionoperatorthatdo not requireV(.r. 0) to be explicitl_y
rvrittenasa 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)
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
J5
34
order of appearancedoes not t.natter).Why do they not conrmute'lBecauseI

containssecondderivatives
n'ithrespect
tothecoordinates
on,
{q , } that I' depends
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 rvenotedis 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
(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 appro.ximated
in terms of the f and I/ exponentialoperatorsas follows:
rrH\
/ \exp
ft /-.*pt,-.
. -t f- t-'F- V
- ln. *\ p ( -/
irr'\
irr\
a /.-o(_;/
(r.e_r)
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 potential z, so this stepis valid for any and all potentials.The ei_eenfunctions
of r :
-n-
*1
,^
rt
/ tntd'/ctq'
arc
, ! , , ( q ) : ( * )*' "r ( T )
( 1.e6)
andthey obeythe following orthogonality

f
V i , t a t t l r , , ( q t :d q3 r p - p l
(r . 9 7 )
rL,.t,t
trlr,",tt1
\lp = |rq - q t.
(r . e 8 )
J
relations
andcompleteness
J
Writing V(q) as
v ( q ) : I A u- ( ] ' ) v ( q ' ) d q , .
(1 . e 9 )
andusingthe aboveexpression
for d(q - q') gives
rr(q) :
| |
v,,u,,,t';,,q'
)rtt(q'ytq'ttp.
(1.100)
theexplicitexpressions
Tlreninsertin-e
for tlr,(c1)andr!
1:
;(q' ) in termsof ,,ft
,,1c1
r'z
pr7
exp(i
0 l2ir 1t
/fi) -erves
.
Q
t ' 7 t :f f l
JI \;
I tr:
' * o1( ;i l7 r 4( 1; ,7) 1 r :. . - o/ ( -i p# u) t Q r 't1' t ' 1 ' t p r r r 0 r t
Now.allor.ving
exp(-i r T lIt)to act on this form for W(r7)produces
/ ; ' , ' r t i \ /I
\''
. . P/ ( i r T )\ w t q , :r r
n
JJ . ' p ( ' # l l r ; t
^ . *' oL[ ? , u : , ,, l f : ) ' ' ' * , r , r o r , r , ( r r 0 2 )
h
) \ h t
The integralover p abovecan be carriedout analyticallyanclgives
. * P/(
1 m r : /
irT\.
f i n r q _ 4 ' t : \l t t t , t ' ) , t " t
n ) q , , t , : ( : r , r , ) 7 . * oL
,"
rr.l03r
So, the final expressiontbr the short-time propagatedwave function is

v"{' ,,r ."r-) ": .u* L
o[-irli'l
t f , n t \ ' t f - . ^ f i n t 1 t- 1( t 7 : 1
(.,,r/
/r-j
7.*pL
,*
{1.10+)
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.
35
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 trrnevarvrngpotentialI1t 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
\a"t'
)t(r't')*
L i t l t ( x " r ' ) :E f ( ' r " r ' )
(1 10-5)
The task at hand is to solve the aboveeigen'alueequationto deternrine

the
"allorved"
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'rasaproduct U(r. -r'): l(.r)BLr,). Substitution
of thisforrnintotheSchriidinger
equarion,
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 independent
ofboth
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 ztn
dx.
(1.107)
- i l b^ - , f B = r ) ' '
2m
ai
(l'lo8)
and
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[,,.
(+)"']
B(,r'):.*p[,r,
(ry)"]
.
ano
'-l
|
/ 2 n E .t ' - |
expl-ilt -.1
|
\ t r /
L
l
a n d . ^ o [ - (, ,+ ) " 1
L
(l.t09t
( rr o )
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
solutionsare obtainedfor eachequationbecausethe,r- and

Trio independent
equationsarebothsecondorderdifferentialequations
Schrodinger
(i.e..
.r.-space
differential
equation
order
has
two independent
solutions).
a second
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
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 .
w h e t h e rt h e e i g e n v a l u e w
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
ofthe energies
alongbothcoordinates
speaks
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
l',
[-,,{i+)
(r.ll )
one is allowedto linearlycombinesolutionsof the Schrodinger

equationthat
havethe sameenergy(i.e.,are de,eenerate)
becauseSchrcidinger
equationsare
'71
Jd
li,ear differentiarequations'An
analogous
processmust be appriedto g(,r,)
to
achievea functionthatvanishes
at.r,: 0.
B(r -op
.. - / 1 1 :.1
(t+!\"'l -.*"
' Lf,.',
;/
\ t i I l - q \ fr ) L(12,,r,
J
rnr2
Furtherrequirin-e
A(.r) andB(rr) to,,,anish.
respecti'elrrat.r : Z.\ and _ 2,.
_r,
s r i e se q u a t i o ntsh a rc a nb e o b e y e d
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-
,iarE,1i:l
) l - e r n J - i(r; ' ) l = '
r ir . , r
and
,l
f
, 2ntE
i,
[ l - ' r /' ]\1 1 1 6r , r l
e r jP
ir . ( f
'
^
n
L
" ) I,
J
; L- ) ll : ,
Theseequationsareequivalent(i.e..
usingexp(i.r):
.s, '- n
[ , l r1\2( n- t-EF; -l :)l
l-
cos-r,* i sin_i,)to
r l a i E ,l r : l
l = . i n l z(' r i /
J
L
J:u
rrr4r
rr'ir5t
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
in space).
one concludesthat the energiesE,
a'd.E, canassumeo'ly'alues that
obey
t 1,,, tr
, l/2
z,{1+rI
=r,o.
\ / r /
. 1 2 n E ,\ r ' 2
r'I
:n,r,
' .l - /l
\
f
(t.ll6)
(1.t17)
, - nlr2rt
^r
(l.rl8)
zilr Li
t ff nu
d
t,
nln2tl
T;8.
uith
n\
and
t l , = 1 . 2 . 3 , . . . ( l . l1 9 )
It is important to stressthat it is
the imposition of boundary conditions,
expressingthe fact that the electron
is spatia'y constrained that gives
,se
to
quantizedenergies.In the absence
of spatialconfinement"or wjth confinement
only at;r : 0 or Z, or only at y _
0 or 2.,, quantizedenergieswould
rot be
realized.
In this exampre,confinementof
the erectronto a finite interval
along both
the 'r and 'r" coordinatesyields energies
that are quantizedalong both axes.
If
the electronis confined"t:lg:l".oJrdinur.
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,.
or
at neirherpoinl).thenthetoralenergy
E liesin th,
isquantizld
u,i r, i, ""t.Anarogs
orsuch
;:Tl'.::T;:li.*r;:,TiffT
iinear triatomic morecurehus
mo.i than enouj energy in one

of its bonds to
ruprureit but not much ener,{yin the other bond; the first bond,sener-evlies in
the continuum.br"rtthe secondbond'senergyis quantized.
moreinteresting
Perhaps
is thecasein whichthebondwith the higherdissoci_
is
ercited
to a levelthatis not enoughto breakit but that is in excess
ationenergv
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
of internalvibrationalenergyrelaxation(IVR) givingriseto unimolecular
speaks
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 depend 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
'
t r' -_ :
( r . 12 0 )
2nLi
n:n-lr
( r .r 2 l )
tnt Ll.
E:E,+8,+tr/o.
1.t22)
y ' (r ,: ( + ) ( # ) ' L * o ( " F- .)* o ( # ) ]

1
\ :
, : , ,
.[.-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,{)
NormalizationallowsltL(x , y)r2to be properlyidentifiedasa probabiliry

density
for findingthe electronat a point-lr.r,.
?a
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
p(-r. corresponding
to classicallyinterprettheprobabilities
to the
-r,)
abovequanturn\4'avefunctionswill resultin failure.As in the one-dinrensionai
case.theclassicalP(.:r'.
alongslicesof fixed.r-andvaryinu_i,
1,)wouldbe constant
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.
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
1 . 4 . 4Q u a n t i z e d
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.
classicalaction(denoteds) of a particremovingwith momentump
Theso-called
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 whichtheHamiltonianis 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 ,: +
2n
ti ;;t: - r
tttt
;:
tt.Y-
- + + v t y t 1v l v t
2n
fi a2
I'{.t)- :-:-;
llll
* l'( r').
dl'-
(r.127)
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)),
, / =t t-t l b - , - Y l . v l l ;
Pt=
(r . r 2 8 )
(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,
:
fi:rf
J,,,,,
t f2n1E,- v(t))rr *
(1.13())
f.tfxt
t
vtrt))t/.v.(r.l-ll)
Jr,,,, Jrm@,-
41
42
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.td q: r i l r
( , : l . ] . 3 . : 1. . . ) .
(1.132)
Appliedto eachof the independent

coordinates
of the trvo-dirnensional
particlein-a-boxproblem,this expression
reads
l,=L
n . , l t= |
J.-o
n,h:
f,=t
Jr:0
-'r
- !f/x(l'
, 2 t n ( E , - I ' ( , r ) )d t + |
- l, = r.
r
Jr(.rD./r.
(l ljj)
f,t
t t 2 m ( E -, 1 " ( . r . t) l)r + |
* r , 1 i 1 E _ t 1 r y 1, l r .
il.13.1)
"lt:t,
Notice that the signs of the niomentaare positivein each of the first inreg r a l sa p p e a r i n a
g 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
6ri l-;
(n'h\2
s nL l
(r.r37)
(1.138)
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,
lo't=o""
(1.r3e)
hasbeenusedto obtainthe result.

Theuseof actionquantizationasillustratedabovehasbecomea very important
tool. It has allowed scientiststo make great progresstoward bridging the gap
betweenclassicalandquantumdescriptionsof moleculardynamics.In particular,
quantalaction
suchastrajectories
andthenappending
by usingclassicalconcepts
people
have
been
able
to
develop
so-called
modelsof
semi-classical
conditions.
In suchmodels,oneis ableto retaina greatdealof classical
moleculardynarnics.
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
modelfbr vibrationof a diatomic
later.which servesas the simplestreasonable
the totalenergyas
moleculeAB. one expresses
e:{+\,'
tlt
(l.l.ro)
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
describing
thebondbetweenA andB. r is thebond-length
displacement.
constant
The quantizedactionrequirement
andp is themomentumalongthebondlen-eth.
thenreads
, h: I pd :, I l ' , ( ' -1 , ' ) ] ' ' , ,
(l.l.1l)
T h i si n t e - u r a
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
rightturningpointsof theoscillatorymotion.andbackagainto form a closedpath.
expression
Carryingout this integraland equatingitto nh givesthe followin_q
for thc energyE:
,
, . 1 2
I I I K \
6-:,,. l-l
::r
(1.142)
\lL/
rvherethe qLlantumnunrberri is allorvedto assumeintegervaluesrangingfrom

n : 0. l. 2. to infinitv.The problemrviththisresultis thatit is wrong! As experimentaldataclearlyshor'",.
thelowestenergylevelsfor thevibrationsof a rnolecule
do not haveE :0: thevhavea "zero-point"energythat is approrimatelyequal
Lo I l2( h l21 11.1;
conditionyieldsenI p\ti: . So.althoughthe actionquantization
ergieswhosespacings
in agreement
rvith laboratorydatatbl lorvarereasonablv
energystates(e.g..suchstateshaveapproxirnately
constantspacings),
it fails to
predictthe zero-pointenergycontentof suchvibrations.As we will seelirter,a
properquantumrrechanicaltreatmentof the harmonicoscillatoryieldsenc'rgies
of the ibrm
"
(1.143)
E : (,,.:) (*)(:)
which differs from the oction-bascdresult by the proper zero-point energy.
43
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-lb
rntegerquantumnumbersdoesnot onlv occurin theharmonicoscillator
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 concludesthatonlyintegralmultiplesoffi canbe'.allowed"valuesofthe:-cornponent
of angularmomenturn.
Experimentalry,,
onemeasures
the:-componentof an anmomentum
placing
bi,
the systempossessing
-eular
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.
whenelectrons,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
angularmomentais not consistent

with the observation
madeearlier
half-integer
that @and Q + 2;r correspondto exactlythe samephysicalpoint in coordinate
u'hich,in turn,impliesthatonly full-integerangularmomentaarepossible.
space,
The resolutionof the aboveparadox(i.e., horv can half-integerangularmomentaexist?)involvedrealizingthat someangularmomentacorrespondnot to
the r x p angularmomentaof a physicalmassrotating.but. insteadareintrinsic
propertiesof certainparticles.That is, the intrinsicangularmomentaof electrons,protons,and neutronscan not be viewed as arising from rotationof some
massthat comprisestheseparticles.Insteadsuch intrinsic angularmomentaare
"built in"
characteristicsof theseparticles.For example.the trvo
fundamental
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 eleca proton has I l2h and -l l2li states,as do neutrons.All such
tron. Analogousl,v,
half-integerangularmomentumstatescan not be accountedfor using classical
mechanicsbut are knorvnto arisein quantummechanics.
45

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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

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

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

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

where.),is the crest-to-crest

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

Hence.the wavesare quantizedin two dimensionsbecausetheir wavelengths

hlp in the aboveequation.one finds

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.

t/2k( q1- ,tl)

The quanturnmechanicaloperatorassociatedwith this

Suchan operatorwould occurwhen,for example,one

and the correspondingoperatoris

The r--componentof the dipole moment for

for which the quantttmoperatoris

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

in which the X7 arecalledeigenfunctions

So. we saythat exp(a_r,)

wherei 7 is oneof theeigenvalues

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

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

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

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

+ l r ^ - 't - /_J t.t.t ? ,,"

wherethe indicesi andj are usedto label the l0 electronswhose30 Cartesian

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

NoticethatH is a secondorderdifferentialoperatorin thespaceofthe 39 Cartesian

- 1\- "' - \- Z,e:w

The Hamiltonianin this casecontains/ nowhere.An exampleof a casewhere11

is addedto the Hamiltonian.Here,xo and.,videnotethe.r coordinatesof the

and the full wave function can be written as

For the aboveexample,the time dependence

In summary,wheneverthe Hamiltoniandoes not dependon time explicitly,

H : t l - , iz n tri t'q--: l \ - - " ' - ' t a l

H : -\ - l - l 'r tit , ": t -, 1*: 1 t ' ' ' - r'Z{

producesas its eigenvalues.

energresErGl,) that dependon where the nuclei are located(i.e., the

Minimum for reactant

Although this plot has more information on it than we shall discussnou'.

nell as the n --+ z* and ir --->lr*electronicstatesand their vibrationallevels.

1.3 Yourfirst applicationof quantum mechanics- motion