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F:ma (l.l)
nt : 24 tinp (1.2)
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.
)":hl(2m"E)t'2. (1.3)
),:hlQmE)1t2, (1.4)
l,.inm
- c
a h
c a
ot c
c
I VisibleI
*.'{fllllrilt-Irffi
frlllill ""'-*,,-onllrll spectrumof atomic
Emission
Anarvsis Paschen h y d r o g e nw i t h s o m e
lrrn lines repeatedbelow to
illustrate t h e s e r i e st o
Llf Brackett w h i c ht h e y b e l o n g .
-
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
2 t r r: n ) . . (1.7)
y :1nhl2n)2 /(m"Ze2) (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
hv=R(tlni-rlni) (l.lr)
So. nou, rve havesome idea why the Newton equationsfail to accountfor
the dynan.ricalnrotionsof light and small;lartrclessuchas electronsand nuclei.
We seethat extraconditions(e.g..the Braggconditionor constraints on the de
Brogiieu'avelength) couldbe imposedto achievcsome degree of agreenrenlu'ith
experimental observation. u'estill arelcft wonderingr.ihattheequations
Hou'e'u'er,
are that can be appliedto properlydescribesuch motior.rs and why the extra
conditions areneeded. It turnsoutthata ner.r'kind of equationbasedon cornbining
u'aveandparticleproperties neededto be developed to address suchissues. These
arethe so-calledSchrddinger equationsto ri'hichwe no\\'tunr our attention.
As I saidearlier.no one hasvet shownthat the Schrodi-qer equationfollou,s
deductivelirfrom somen.rorefundamentaltheory.That is. scientistsdid not de-
theypostulatedit. Sorre ideaof hou'the scientists
rive this equatiotr; o1'thatera
"dreamedup" the Schriidinger equationcan be had by exan-rir.ring tirre and
thc
spatialdepcndence thatcharacterizes so-called travelingu,aves. lt shouldbe noted
that the peoplervhoworkedon theseproblcmskneu'a greatdcal aboutu'aves
(e.g.,soundw'avesand \\.ater\\'aves)and thc equationsthey obeyed.Moreover.
they kneu' that u,avescould sometimesdisplaythe characteristic of quantized
u'avelenqths or fi'equencies (e.9..fundamentals and overtonesin soundu'a'"'es).
They'kneu',for example.that r.r,a'u'esin one dinrensionthat are constrainedat trvo
points(e.g..a violin stringheld fixed at tu'o ends)undergooscillatorymotjon
in spaceandtime with characteristic fi'equencies andu'avelengths. For exan.rple.
the motion of the violin stringjust nrentionedcan be describedas havingan
arnplitudeA(r. t ) at a position-r alon-qits len-sthat tinle I gircn by
l ( , 1 -/ .) : , 4 ( . r - . 0 ) c o s ( 2 . ' r y r ) . (1.13)
w h e r en : 1 . 2 , 3 . 4 , . . . T h e equation
t h a t s u c hw a v e so b e y ,c a l l e dt h e w a v e
F u n d a m e n t aaln d f i r s t equation.reads
overtone notes of a
d2,4(x,t) . d2A
v i o l i ns t r i n g . (r . l 6 )
Lll- (l\-
W h y q u a n t u mm e c h a n i c si s n e c e s s a r fyo r d e s c r i b i n gm o l e c u l a rp r o p e r t i e s
v : : ( c l n ) :. (r .r 7 )
or
c: tv. (1.18)
Jt.J /22 \r
;(/.\-
- : - l . l l (1.20)
\ ,\ ,/
andusingthe de Brogliehypothesis
X: hlp in the aboveequation.one finds
,l:.1 .71.2 \l
-:-p-l , | ,a (r.21)
.1.\'- \ tt /
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
/ h \ dA
i ( ^ I ' : E i t ' (1.24)
\tlr / dl
th 1d.4 r lt \:J:A
'\=/ :- (1.2s)
,t, \;/ ,..
,(+)# and
E (r . 2 6 )
and bet."veen
r , 1/t1:d:
D- anc ( 1 . 2| 7
\ 2:r) dt:
or, alternatively.between
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.
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, ( q,- q) ,) l
t/2k( q1- ,tl) (1.29)
l t'i /2 u ,,+
The quanturnmechanicaloperatorassociatedwith this
.F is
t :,I, - +t'(q,-'ti')]
L*,# * )r (,' q;')' (I . 3 0 )
t: GiPvt-)'tP,i), (r.31.)
f
-/= I ..'\'
t : -t,.,:.Iu
(',* - r',+) ( r. 3 2 )
If one transformsthesecartesiancoordinatesand
deri'ativesinto polar coordi_
nates,the aboveexpressionreducesto
a
F--iltf ( 1. 3 3 )
i?' 3Qi
The r--componentof the dipole moment for
a coilection of 1y'particleshas a
classicalform of
'p -- ./--
\- Z1exi, ( r.34)
T h e S c h r o d i n g eer q u a t i o na n d i t s c o m p o n e n t s 12
F: I Z,exi, (r .3s)
F x ,: u , x , (r . 3 6 )
(1.37)
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.
Fxt : )",x1. (r . 3 8 )
wherei 7 is oneof theeigenvalues of F. we know thatthevaluei7 wili be observed
if thepropertyF is measuredwhile thernoleculeis describedby thervavefuncrion
'4t:
X.i.ln fact,oncea measurement of a physicalquantityF hasbeencarried
out and a particulareigenvalue).i hasbeenobserved-the system'srvavefuncrion
v becomesthe eigenfunction1, that correspondsto that eigenvalue. That is, the
T h e S c h r o d i n g eer q u a t i o na n d i t s c o m p o n e n t s 15
F G = G F (1.39)
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
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.
H t U : i 7 16 r y 1 ' 6 , . (1.43)
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:
)- f
Z,rX,,f.cos((r/ e;r7E
cos(rr-rr) (1.47)
)
is addedto the Hamiltonian.Here,xo and.,videnotethe.r coordinatesof the
ath
nucleusand the7th electron.respectivelv.
V ( q , , t ) = W ( qi ) F ( t ) (l.4E)
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
V ( q 1 )i t t 0 F l ' d t: F Q ) H V ( qt t . (1.49)
D i v i d i n gb y V ( q 1 1 F ( tt)h e ng i v e s
F t t i ht ) F l i t r t : W i [ H , ! ( 4)i] . (1.50)
SinceF(l ) is only a functionof time t. andtU(q 1)is only a functionof the spatial
coordinates lq 1], andbecausethe left-handand riglit-handsidesmust be equal
for all valuesof t and of lq il, both the left- and right-handsidesmust equala
constant. lf this constantis calledE. the two equationsthatareernbodiedin this
separatedSchrodingerequationreadas follou,s:
HV(q,): EV(q,). ( l . 5 l)
ifidF(t)ldt: EF(t). il.sl)
Thefirstoftheseequations is calledthetin-re-independent Sclrrodinger equatron: it
is a so-called eigenr,alue equationin u'hichoneis askedto find functionsthat1,ield
a constantmultipleof ther.nselves when actedon by the Hamillonianoperator.
Suchfunctionsarecalledeigenfunctions ofH andthecorresponding coustallts are
c a l l e dc i g . e n r a l u oe fsH . F o re x a m p l ei .f H u e r eo f ' r h ef o r m ( _ l i ' 2 . \ lt ; t :, d Q : -
H" tlrenfunctionsof thc form exp(inrQ)would be eigenfunctions because
I li d: I ln:h:l
,-
- - l
ztra6,1e x p ( i', , i @ ) : l * f crptiirrd,). ll.-i.l)
I [:,r,J
In thiscase.rr 2tt2
12tvtis theeigenvalue. In thisexample.theHarriltoniancontains
the squareof an angularmomentumoperator(recall earlierthat u,'eshou'edtlre
:-cornponent of angularmomentumis to equal-ih d ldQ).
\Vhen the Schrcidingerequation can be separatedto -seneratea time-
independent equationdescribingthe spatialcoordinatedependence ofthe u'ave
function,the ei_eenvalue E mustbe retumedto the equationdeterminingF(t) to
find the time-dependent part of the wavefunction.By solving
once E is known.oneobtains
v ( qi . r ) : w ( q i )e x p ( -i E t l t t ) . (1.56)
F(r) : exp(-irlnt2ti1zll1itt1. (l . s 7 )
T h e S c h r o d i n g eer q u a t i o na n d i t s c o m p o n e n r s
tv
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.
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 Secondorder n
saddlepoint
potentialenergysurface
\ralley-ridgc
s h o w i n gl o c a lm i n i m a , 0.5
i n f l e c t i o np o t n t
transitionstatesand Minimum for reactant
p a t h sc o n n e c t i n g
them.
1 . 3 . 1C l a s s i c aplr o b a b i l i tdy e n s i t y
I would like you to imaginewhattheprobabilitydensitywould be for this particle
moving with total energyE and with I/(,r) varying as the threeplots in Fig. L6
Three
characteristic potentials
showing left and right
c l a s s i c at lu r n i n gp o i n t s
at energiesdenotedby
t h e h o r i z o n t aIli n e s .
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
0 : p : ( 2 m ( E - I ' ( . t ) )r r. (1.6i)
Classical
ty plotsfor the
three potentialsshown
i n F i g .1 . 6 .
M o t i o no f a p a r t i c l ei n o n e d i m e n s i o n 23
slorvly.it spendsmore time and P(.r) is larger.For the plot on the ri_eht,/(,r)
"box".
is constantwithin the so the speedis constant.hencep(.r) is constant
fLrrall .v valuesrvithinthis one-dimensionalbox. I ask that you keepthesepiots
in nrind becausethey are very difrerentfrom what one finds when one solves
the Schrcidinger equationfor this sameproblem.Also pleasekeepin mind that
these plots representwhat one expectsif the particle were moving accordingto
classicalNewtoniandynamics(w,hichwe know it is notl).
1 . 3 . 2O u a n t u mt r e a t m e n t
To solve tbr the quantLlmmechanicalwavefunctionsand energiesof this same
problem,we first write the Hamiltonianoperatoras discussedaboveby replacing
n Ov -lll(l /Ll.\".
h' ,t:
Il:-'--l+l'rrr (1.63)
lilt tl.\-
1 . 3 . 3E n e r g i e sa n d w a v e f u n c t i o n s
The secondorderdift-erential
equation
il tlllr
- -;-. -t tr/\r)tlr : Etlt (1.6.+)
^
lnt dr'
hastwo solutions(becar.rse
it is a secondorderequation)in the regionbetrveen
"r:0andx:L:
ty': .1sintA.r)
+ B cosrfr.r'.y. (1.66)
z4 T h e b a s i c so f q u a n t u mm e c h a n i c s
B =0. (1.67)
E : n1r2rt
l(2mt). (r . 7 0 )
This result saysthat the only energyvaluesthat are capableof grving a wave
function ry'(x)that will obey the aboveconditionsare thesespecificE r.alues.In
otherwords,not all energyvaiuesare"allowed"in the sensethattheycanproduce
ry'functionsthat are continuousand vanishin regionswhere z(x) is infinite. If
one usesan energyE that is not one ofthe allowedvaluesand substitutesthis E
into sin(*;r),the resultantfunctionwill not r,anishat x : L.I hopethe solutionto
this problemremindsyou of the violin stringthatwe discussedearlier.Recallthat
the violin stringbeing tied down at x : 0 and at -r : z gaverise to quantization
of the wavelengthjust asthe conditionsthat ry'be continuousat;r-: 0 ar.rdx : Z
gaveenergyquantization.
Substitutingk : nn /L into ry': I sin(k,r)gives
t: l l t t r ) l i , / . t: l . -1t : s i n 2 t r xz I L ) t t x . 0.72)
J ;l
where the integral rangesfrom r : 0 to x : L. Looking up the integral of
sin:(a,rI and solving the aboveequationfor the so-callednormalizationconsranr
I gtves
A : (2lDtt2 (1.73)
andso
1 . 3 . 4P r o b a b i l i t yd e n s i t i e s
Let's now look at sorne of the wave functionsv(.r) and compare the proba-
bility densitieslv(.r)ir that they representto the classicalprobabilitydensities
discussedearlier.The n : 1 and n : 2 wave functions are shown in the top
of Fig. 1.8.The corresponding probabilit-v
densitiesare shownbelowthe wave
functionsin two tbrmats (as n--vplots and shadedplots that could relateto the
flashinglight way of monitoringtheparticle's locationthatu'e discussed earlier).
A more completesetof r.vavefunctions(for izrangingfrom 1 to 7) are shownin
F i e .1 . 9 .
zo T h e b a s i c so f o u a n t u mm e c h a n i c s
,ffi'ffi
n:2
The two
lowest wave functions
and probability
densities.
{
V.
m,axffita;,;*r
25 mau,*ffiu,,*;r
Node
t6
9
Seven
lowestwave functions I
andenergies.
I
M o t i o n o f a p a r t i c l ei n o n e d i m e n s i o n
27
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
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
I
0.9 11 iI h
0.8 I \ 1 I
0.7 r
^. (\A
5
r! 0.5
V o.c I
I
I
0.3
0.2 I I
0.1 I
I
Ouantum
probabilitydensityfor I I
n : 7 s h o w i n gs e v e n
peaksand six nodes.
0 v rJ \
xlL
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 29
o= lr',t,,,r',t,,,
a, (1.77)
where the complex conjugate* of the first function appearsonly when the ry'
solutionscontainimaginarycomponents (you haveonly seenone suchcasethus
far - the exp(ill @) eigentunctions
of the:-componentof an-qular
momentum).It
is commonto write the integralsdisplayingthe normalizationand orthogonality
conditionsin the fbllorvineso-calledDiracnotation:
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)
F r . L: 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
energyEn : n2r2h2lQmLz),the time-dependent u'avefunctionis
r): (?)"',inff*r(-?),
v(x. (1.82)
which can be generated by applying the so-called time evolution operator U(l' 0)
to the wave function at I : 0:
V(x.r) : U(r,0)v(,r,0) (1 . 8 3 )
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::
rv(r j{(;),'",(+)
. (;),,'',(?)
-'(?).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 u.l
d o.E r I--r\ 0 ^ --
/ i I \
E t,.o
/f 06 !_t
\ f_' t I
l i . . - lt .l 0.i
I
.- 04
(1.-l / l
_0.1 I
^
{ { ()l t
> {)l
t
t
= = 0 I
\ j
( 1I.
-t ! 7
-0:
X,L
1.6
{ ^l i. { -1^
t: t.l / \ I
f \
J 1 6l
I
I
0 N i \
.\
0.6
t:
.=
I
I
1).1 I a
: d a
|I,
vi )
L_] -
jflff r h e n : 1 a n d n : 2 w a v e f u n c t i o n st,h e i r
s u p e r p o s i t i o na,n d t h e
a n dt i m e - e v o l v ep
d r o b a b i l i t yd e n s i t i e so f t h e
superposition.
.r = L. The issueof horv the particle in the latter statemovesfrom being near
r = L f 4 to x : 3 L l4 is not somethingquantummechanicsdealsrvith.euanfum
mechanicsdoesnot allow us to follow the particle'strajectory.which is what we
needto know whenwe askhow it movesfrom oneplaceto another.Nevertheless.
superposition wavefunctionscan offer"to someextent,the opportunityto tbllow
the motionof the particle.For example,the superpositionstatewritten aboveas
2 - r , : 1 2 1 1 1 1s1i n2( l z - r l Z )- 2 - t / 2 Q l L ) t / 2 s i n ( 2 n x l L ) h a s a p r o b a b i l i t y a m p l i -
tude that changeswith time as shown in the figure. Moreover,this amplitude's
major peakdoesmove from side to side within the box as time evolves.So, in
this case.we ciln say with what frequencythe major peakmovesback and forth.
"follorv"
In a sense.this allor.vsus to the particle'smovements.but only to the
extent that'"ve are satisfied with ascribingits locationto the positionof the major
peakin its probabilitydistribution.That is, we can not really foilor.vits "precise"
location.but we can follor,vthe location of where it is very likely to be found.
This is an importantobservationthat I hopethe studentwill keepfreshin mind. It
is alsoan importantingredientin modernquantumdynamicsin which localized
wavepackets,similarto superposed eigenstates, are usedto detailthe position
andspeedof a particle'smain probabilitydensitypeak.
Thc-aboveexampleillustrateshow one time-evolvesa \ryavefunctiontharcan
be expressed as a linearcombination(i.e..superposition) of eigensrates of the
problem at hand. There is a large amount of current eftbrt in the theoreti-
cal chemistrycommunityaimedat developingelicient approximations to the
exp(-i t H lll) evolutionoperatorthatdo not requireV(.r. 0) to be explicitl_y rvrit-
tenasa sumof eigenstates. This is importantbecause, for mostsystemsof direct
relevanceto molecules,one can not solvefor the eigenstates; it is simply too
difficult to do so. You can find a significantlymore detailedtreatmentof this
subjectat the research-level in my TheoryPageweb siteand my el,tIC tertbook.
However.let'sspenda little time on a brief introductionto what is involved.
The problemis ro expressexp(-itHlh)V(qr), whereV(qr) is some initial
wave function but not an eigenstate,in a manner that does not require one
to first find the eigenstates{V7} of H and to expand V in terms of these
eigenstates:
v:fc,w, ( 1.e0)
J
:
"t (-#) v@,)
1,,*,*,(-+) (l.er)
*'(-f):*'(-+)
*'(-f) (l q2)
is not fully valid as one can seeby expanding all threeofthe aboveexponential
f a c t o r sa s e x p ( . r ) : I * . r - + x 2 / 2 ! * . . . . a n d n o r i n _tqh a l t h e r $ , os i d e so f t h c
aboveequationonly a-eree if one canassulnethatTl': I'L u,hich.as rvenoted-
is not true.
In mostr.nodern approaches to time propagation. onedividesthe time interval
r into nrany(i.e..P of them) small time "slices"r : t / p. onc then expresses
the evolutionoperatoras a productof P short-timepropagators:
itH\ rrHl
e x /p ( - , , : . * o /l - - ) . - o ( -I ; , i) t. H- n\ ( - r i r H t
/ ; )
irtl\lr
: I t
(r.e3)
L ' * n \ -t / l
If one can developan efficient rneansof propagatingfor a short time r. one
can then do so over and over again P times to achievethe desiredfull-time
propagation.
It can be shown that the exponentialoperatorinvoll'ing 11 can betterbe ap-
pro.ximated in terms of the f and I/ exponentialoperatorsas follows:
rrH\ . -t f- t-'F- V
/ \-
exp l - ln. *\ p ( -/ irr'\ r irr\
(r.e_r)
ft /-.*pt,-. a /.-o(_;/
So. if one can be satisfiedwith propagatingfor very short tirne ir.rtervals
(so that
the rl term can be neglected),one can indeeduse
*'(-#)-*p(-+)-'(-T) (r.e5)
/ tntd'/ctq' arc
v ( q ) : I A u- ( ] ' ) v ( q ' ) d q , . (1 . e 9 )
rr(q) : )rtt(q'ytq'ttp.
v,,u,,,t';,,q' (1.100)
| |
Tlreninsertin-etheexplicitexpressions
for tlr,(c1)andr!
r'z ;(q' ) in termsof ,,ft 1:
,,1c1
0 l2ir 1t pr7
exp(i /fi) -erves
. I tr:
Q t ' 7 t :f f l |
' * o1( ;i l7 r 4( 1; ,7) 1 r :. . - o/ ( -i p# u) t Q r 't1' t ' 1 ' t p r r r 0 r t
JI \; J
Now.allor.ving
exp(-i r T lIt)to act on this form for W(r7)produces
. . P/ ( i r T )\ w t q , :r r / ; ' , ' r t i \ /I
\''
n JJ . ' p ( ' # l l r ; t
^ . *' oL[ ? , u : , ,, l f : ) ' ' ' * , r , r o r , r , ( r r 0 2 )
) \ h t h
The integralover p abovecan be carriedout analyticallyanclgives
. * P/(
irT\. 1 m r : / f i n r q _ 4 ' t : \l t t t , t ' ) , t " t
n ) q , , t , : ( : r , r , ) 7 . * oL ," 1
. rr.l03r
So, the final expressiontbr the short-time propagatedwave function is
t f , n t \ ' t f - . ^ f i n t 1 t- 1( t 7 : 1
v"{' ,,r ."r-) ": .u* L
o[-irli'l (.,,r/ {1.10+)
/r-j 7.*pL ,* lVtt1'td,l.
whichis theworkingequationoneusesto computeV (q , t )knowingV (4). Notice
thatall oneneedsto kno."r,
to applythis formulais the potentia1 v (q) ateachpornt
ln space.one doesnot needto know anyof the eigenfunctions of the Hamiltonian
to apply this method.Howe'u'er. one doeshaveto use this formula over and over
agarnto propagatethe initial wavefunction throughmany small time stepsr to
achievefr"rllpropagationfor the desiredtime intervalt : pt.
Becausethistypeoftime propagationtechniqueis a very activeareaofresearch
in thetheorvcommunity.it is likely to continueto berefinedandimproved.Further
discussionof it is beyondthe scopeof this book, so I will not go further in this
direction.
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 trrne-
varvrngpotentialI1t at all pointsin this plane.The pertinenttinre-independent
S c h r o d i n g ec rq u a t i o ni s
-t t /a t a t\..
+ 'drt L i t l t ( x " r ' ) :E f ( ' r " r ' ) (1 10-5)
\a"t' )t(r't')*
The task at hand is to solve the aboveeigen'alueequationto deternrine
"allorved" the
energystatesfor this electron.Becausethereareno termsin this equa_
tion thatcouplemotionin the; and l directions(e.g..no ternlsof the
form,t,-r.b
or Sldx 0/Ev or x 0/8v),separation of'u'ariabres
canbe usedrowrite y'rasaprod-
uct U(r. -r'): l(.r)BLr,). Substitution
of thisforrnintotheSchriidingerequarion,
followedby collectingtogetherall r-dependentandall
terms,
_r'-dependent _qrves
rf 1a]A rt ta2a
2*7ar;- (l'106)
2-E *:E-rtt'
Since the first term contains no r,-dependence and the second contains no
x-dependence. and becausethe right sideofthe equationis independentofboth
x and -r,,both terms on the left must actuallybe constant(thesetwo
consranrs
are denoted E" and Er', respectiveiy).This observationailows two
seDarare
Schrcidinger equationsto be written:
rt . alA
- - / - ' - - F -
(1.107)
ztn dx.
and
A(x):*o[,,.
I r '-l
. | / 2 n E .t ' - |
(+)"'] ano expl-ilt -.1
\ t r /
| (l.t09t
L l
B(,r'):.*p[,r,
(ry)"] a n d . ^ o [ - (, ,+ ) " 1 ( rr o )
L \ r )
F r e ep a r t i c l em o t i o n si n m o r e d i m e n s i o n s '71
1 , 4 . 2B o u n d a r yc o n d i t i o n s
T h e b o u n d a r y c o n d i t i o n s ,n o t t h e S c h r o d i n g e re q u a t i o n ,d e t e r m i n e
w h e t h e rt h e e i g e n v a l u e w
s i l l b e d i s c r e t eo r c o n t i n u o u s .
li,ear differentiarequations'An
analogousprocessmust be appriedto g(,r,)
achievea functionthatvanishes to
at.r,: 0.
f , 2ntE ,l
e r jP ir . ( f i, ' ^ [ l - ' r /' ]\1 1 1 6r , r l
n
L " ) I, J ; L- ) ll : , rrr4r
Theseequationsareequivalent(i.e..
usingexp(i.r): cos-r,* i sin_i,)to
.s, '- n
[ , l r1\2( n- t-EF; -l :)l l- r l a i E ,l r : l
L l = . i n l z(' r i / rr'ir5t
J L J:u
Knou,ing t h a rs i ng v a n i s h e a
ste- nn,forz : l. 2.
3 . . . . l a l t h o u g ht h es i n ( z r )
function'u'anishes for n :0, this function'anishes
for all -t or.r,,andis therefore
unacceptabre becauseit represents zeroprobabiritydensityat alr points
one concludesthat the energiesE, in space).
a'd.E, canassumeo'ly'alues that
obey
t 1,,, tr , l/2
z,{1+rI =r,o.
\ / r / (t.ll6)
. 1 2 n E ,\ r ' 2
r'I ' .l - /l :n,r,
\ f (1.t17)
^r , - nlr2rt
zilr Li (l.rl8)
nln2tl
d
t ff nu d k
t, - = uith
T;8. n\ and t l , = 1 . 2 . 3 , . . . ( l . l1 9 )
It is important to stressthat it is
the imposition of boundary conditions,
pressingthe fact that the electron ex-
is spatia'y constrained that gives
quantizedenergies.In the absence ,se to
of spatialconfinement"or wjth confinement
only at;r : 0 or Z, or only at y _
0 or 2.,, quantizedenergieswould
realized. rot be
In this exampre,confinementof
the erectronto a finite interval
the 'r and 'r" coordinatesyields energies along both
that are quantizedalong both axes.
the electronis confined"t:lg:l".oJrdinur. If
1.g., u.t*".n 0 < x < 2..) bur not
along the other (i.e., Blu) is eitherrestrictea
ioi,anist aty - 0 or at .1,: L,.
at neirherpoinl).thenthetoralenergy or
E liesin th,
isquantizld
u,i r, i, ""t.Anarogs
orsuch
iinear triatomic morecurehus
;:Tl'.::T;:li.*r;:,TiffT
mo.i than enouj energy in one
of its bonds to
F r e ep a r t i c l em o t i o n si n m o r e d i m e n s i o n s ?a
ruprureit but not much ener,{yin the other bond; the first bond,sener-evlies in
the continuum.br"rtthe secondbond'senergyis quantized.
Perhaps moreinteresting is thecasein whichthebondwith the higherdissoci_
ationenergv is ercitedto a levelthatis not enoughto breakit but that is in excess
ofthe dissociationenergyofthe weakerbond.In this case.onehastw.odegenerate
states:(i) the stron-sbond havinghi-ehinternalener-qy and the weak bondhaving
low energy(/r). and (ii) the stron_e bondhavinglittle energyandthe weakbond
ha'ing more thanenoughenergyto ruptureit (tL). Althou_eh an experimenrmay
preparethe moleculein a statethat containsonly the former component(1.e.,
rlt : Crltr -f C1r2.with cr - l. c: : 0), coupringbetrveenthe two degenerate
functions(inducedby terms in the HamiltonianH that havebeen ignoredin
definingry'1and ry'2)usuallycausesthe true wave function W : exp(_il Hih){.,
to acquirea componentof the secondfunctionastime evolves.In sucha case,one
speaks of internalvibrationalenergyrelaxation(IVR) givingriseto unimolecular
decomposition of the nrolecule.
1 . 4 . 3E n e r g i e sa n d w a v e f u n c t i o n sf o r b o u n d s t a t e s
For discreteenergy revers,the energiesare specifiedfunctionsthat de-
pend on quantum numbers, one for each degree of freedom
that is
quantized.
- ,l:iT- tT
' ( r . 12 0 )
2nLi
n:n-lr
t r' -_ :
L
tnt Ll.
- . ( r .r 2 l )
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,{)
t
NormalizationallowsltL(x , y)r2to be properlyidentifiedasa probabiliry
density
for findingthe electronat a point-lr.r,.
40 T h e b a s i c so f q u a n t u m m e c h a n i c s
rffi)
wl
Plots of the
( a )( 1 , 1 )(,b )( 2 , 1 )(,c )
{ 1 , 2a) n d \ d l Q , 2 lw a v e
f u n c t i on s .
1 . 4 . 4Q u a n t i z e d
a c t i o nc a n a l s o b e u s e dt o d e r i v e
e n e r g yl e v e l s
Thereis anotherapproachthat canbe usedto find energylevelsand is especially
straightforwardto use for systemswhose Schrodingerequationsare separable.
Theso-called classicalaction(denoteds) of a particremovingwith momentump
alonga pathleadingfrom initial coordinateq1at initial time ri to a final coordinate
q r . a rt i m er ; i s d e f i n e db y
s= (r.125)
/*"'R.o{.
Here.the momentufirvectorp containsthe momentaalong all coordinatesof the
system.and the coordinatevector q likewisecontainsthe coordinatesalong all
suchdegreesof freedom.For example,in thetwo-dimensional particle-in-a-box
problemconsidered above,q : ("r..ir)hastwo components
as doesp : (p,.p,,),
and the action integralis
(r.r26)
In computin-u suchactions,it is essential
to keepin mindthesignof themomentum
as the particlemovesfrom its initial to its final positions.An examplewill help
clarify'thesematters.
Forsystemssuchastheaboveparticle-in-a-box examplefor whichtheHamil-
tonianis separable,the actionintegraldecomposes into a sum ofsuch integrals.
one fbr eachdegreeof freedom.In this trvo-dimensional example,the additivity
of H.
H : t i ,- H ,: + - + + v t y t 1v l v t
2n 2n
ti ;;t: - r fi a2
tttt
;:
tt.Y-
I'{.t)- :-:-; * l'( r'). (r.127)
llll dl'-
p, : +r/2i(.1rlo)), (r . r 2 8 )
, / =t t-t l b - , - Y l . v l l ;
Pt= (1.129)
the signs on p, and pr, must be chosento properly reflectthe motion that the
particleis actuallyundergoing.Substitutingtheseexpressions into the action
rntegralyields
s:s,+,s, (1.13())
fi:rf
f f.tfxt
: t f2n1E,- v(t))rr * t vtrt))t/.v.(r.l-ll)
J,,,,, Jr,,,, Jrm@,-
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
s . r n .=
" d f q t = c ' p: t.td q: r i l r ( , : l . ] . 3 . : 1. . . ) . (1.132)
Notice that the signs of the niomentaare positivein each of the first inre-
g r a l sa p p e a r i n ag b o v e( b e c a u s teh e p a r t i c l ei s m o ' i n g f i . o m . r : ( ) t o . r - : 1 , .
a n d a n a l o s o u s lfyo r . t - l t t o t i o na. n d t h u sh a sp o s i r i r en r o n t c n t u l lrrn d n e l a r i r t
i n e a c ho f t h e s e c o n di n r e g r a l s( b e c a u steh e r n o t i o ni s f r o m . r : l , t o - i - : 0
(andanalogously for.r'-motion)and thusthe particlehasnegativenromentum).
W i t h i nt h e r e g i o nb o u n d e db y 0 . - r -< l . : 0 < , r . < 2 , . t h c p o t e n t l avl a n i s h e s "
so i/(x) : l'lr') : 0. Using this fact. and re'ersingthe upperanti lou,erlinrits.
andthusthe si-sn.in the secondintegralsabove.one obtains
'='
n, h : 2 1Zn t, tlt. : 2{r,, tr, L, (1.3
16)
[
- (n,h12
(r.r37)
6ri l-;
- (n'h\2
(1.138)
s nL l
Theseare the sarnequantizedenergylevelsthat arosewhen the u,avefunctron
boundaryconditionswerematchedatx : 0. r : 2., and,l : 0..1,: 1,,. In this
case!one saysthat the Bohr*sommerfeldquantizationcondition.
nh : p.de, (1.r3e)
lo't=o""
hasbeenusedto obtainthe result.
Theuseof actionquantizationasillustratedabovehasbecomea very important
tool. It has allowed scientiststo make great progresstoward bridging the gap
betweenclassicalandquantumdescriptionsof moleculardynamics.In particular,
F r e ep a r t i c l em o t i o n si n m o r e d i m e n s i o n s 43
by usingclassicalconceptssuchastrajectoriesandthenappending quantalaction
conditions.people have been able to developso-called
semi-classicalmodelsof
moleculardynarnics. In suchmodels,oneis ableto retaina greatdealof classical
understandingwhiie building in quantumeffects such as energy quantization.
zero-pointenergies.and interf'erences.
1 . 4 . 5O u a n t i z e da c t i o nd o e s n o t a l w a y sw o r k
Unfortunately.the approachof quantizingthe action does not alwaysyield the
correcterpressionfor the quantizedenergies.For example.when appliedto
the so-calledharmonicoscillatorproblemthat we will study in quantumform
later.which servesas the simplestreasonablemodelfbr vibrationof a diatomic
moleculeAB. one expresses the totalenergyas
e:{+\,' (l.l.ro)
tlt t
w h e r e 4 : m ^ n t B l 0 nA f r r s ) i s t h e r e d u c e d m a s s o f tAhBe d i a t o m . firs t h ef o r c e
constant describing thebondbetweenA andB. r is thebond-length displacement.
andp is themomentumalongthebondlen-eth. The quantizedactionrequirement
thenreads
i sl c a r r i e do u tb e t w e e ny = - ( 2 8 l k ) l ' l a n dC E l k l ' 1 . t h el e f ta n d
T h i si n t e - u r a
rightturningpointsof theoscillatorymotion.andbackagainto form a closedpath.
Carryingout this integraland equatingitto nh givesthe followin_q expression
for thc energyE:
, , . 1 2
I I I K \
6-:,,. l-l (1.142)
::r \lL/