Professional Documents
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Geophysics
Geophysics
(l.l)
(1.2)
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.
(1.3)
(1.4)
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
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)
(1.7)
(l 8)
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
(1.r0)
hv=R(tlni-rlni)
(l.lr)
I
-nt,Z-e*llltr)tl'
(1.12)
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
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)
(1.1.1)
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
(1.19)
andusingthe de Brogliehypothesis
X:
,l:.1
-:-p-l
.1.\'-
/22 \r
. l l
\ ,\ ,/
(1.20)
, | ,a
tt
(r.21)
(1.\'-
(1.22)
or, aiternatively.
-(*)'#: uo
r t 1l\
10
T h e b a s i c so f q u a n t u mm e c h a n i c s
dl
(1.24)
1d.4
:,t,
r lt \:J:A
,..
\;/
(1.2s)
,(+)# and
E
(r . 2 6 )
and bet."veen
r
D-
,
anc
1/t1:d:
\ 2:r) dt:
( 1 . 2| 7
or, alternatively.between
(1.18)
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
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
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
r:,I,
t :,I,
(1.29)
.F is
- +t'(q,-'ti')]
L*,# * )r (,' q;')'
(I . 3 0 )
GiPvt-)'tP,i),
(r.31.)
-/= I ..'\'
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 )
Z1exi,
( r.34)
T h e S c h r o d i n g eer q u a t i o na n d i t s c o m p o n e n t s
Z,exi,
(r .3s)
F x ,: u , x ,
(r . 3 6 )
12
14
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
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 )
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
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)
( 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
(1.:12)
15
to
T h e b a s i c so f q u a n t u mm e c h a n i c s
subsequent
measurementof the secondoperatoru'ill producean eigenvalueof
that operator.but the systemu'avefunction will be changedto beconrean 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.
(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
( r.44)
I'
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
H=E
* #l . : l * - + T l
.+[-*#.:+'#l
.'15)
't7
-tl_ l
a:
'll2n,'dq.;
?,.,"
* 1 l Z , Z n e :\ y
2?
rr.h
;l r!
lnAt
( 1.16)
Z,rX,,f.cos((r/
)- f
e;r7E
cos(rr-rr)
(1.47)
(l.4E)
17
18
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
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)
(1.56)
(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
?,,"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.
,,, l'
(1.59)
(1.60)
tv
20
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
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
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
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
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
(1.6i)
(i.62)
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.\-
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 b a s i c so f q u a n t u mm e c h a n i c s
(1.67)
sin(tr-).
(1.6[i)
(r.69)
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)
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
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)
(1.73)
andso
/(-r) : (2111trt sin(nrx I L)
(r . 7 4 )
lttl L-/lt
(r.75)
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.
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
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
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
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
\
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
l:
ltrlt,,:,/t:/ .a,,:lt'.
(1.16)
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)
29
5U
T h e b a s i c so f q u a n t u mm e c h a n i c s
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)
Ft.r
( r . 8 )l
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 )
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
(1.8+.)
*'''"-l.
n
l
(1 . 8 5 )
, / 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
v ( ;rr1 *: ' ( - # )
['
{,
",'"
' { i ) ' , , " ( T ) - ' ' '(?r)
(?)l
,'G)"'
"',"(?).-'(-+)]
(r.88)
,)r::
j{(;),'",(+)
. (;),,'',(?)
rv(r
-'(?).o, - u,)if,',
(+),'"(?)] o8e)
[ru,
5Z
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
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.
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
.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)
:
"t (-#) v@,)
1,,*,*,(-+)
(l.er)
J5
34
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
*'(-f):*'(-+)
*'(-f)
(l q2)
irtl\lr
(r.e3)
L ' * n \ -t / l
/ \exp
ft /-.*pt,-.
. -t f- t-'F- V
- ln. *\ p ( -/
irr'\
irr\
a /.-o(_;/
(r.e_r)
*'(-#)-*p(-+)-'(-T)
(r.e5)
*1
,^
rt
/ tntd'/ctq'
arc
, ! , , ( q ) : ( * )*' "r ( T )
( 1.e6)
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
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:
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\.
n ) q , , t , : ( : r , r , ) 7 . * oL
,"
rr.l03r
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.
35
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
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')*
(1 10-5)
rf 1a]A rt ta2a
2*7ar;-
(l'106)
2-E *:E-rtt'
rt
. alA
- - / - ' - - F ztn
dx.
(1.107)
- i l b^ - , f B = r ) ' '
2m
ai
(l'lo8)
and
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
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 )
'71
Jd
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
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
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
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)
\ :
, : , ,
.[.-o(
+)-.-,(-i:)]
w i t h n , a n di l , = ! . 2 , 3 , . . .
(L.l:l)
w o . 1 , ) l 2 dt txv : I
( L 12,{)
?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 .
F r e ep a r t i c l em o t i o n si n m o r e d i m e n s i o n s
a 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{.
(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)
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
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
( , : l . ] . 3 . : 1. . . ) .
(1.132)
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
(l.li5)
'='
n, h : 2
1Zn t,
(1.3
16)
(n,h12
6ri l-;
(n'h\2
s nL l
(r.r37)
(1.138)
nh :
p.de,
lo't=o""
(1.r3e)
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
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
(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/
43
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
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
F r e ep a r t i c l em o t i o n si n m o r e d i m e n s i o n s
45