5.

Quantum mechanics in one dimension

Schrdingers equation is the analogue to the wave y 1 y equation of sound, light, water, x = v t , which works for
2 2 2 2 2

all classical waves, that have either a photon associated with it or a pseudo-particle (such as a phonon)

harmonic wave, plane wave is solution to this equation moving to the right
y(x,t) = y0 cos 2 (x/ - t/T) = y0 cos 2/ (x vt)
where v = !"

these functions describe something with physical significance, e.g. the E vector, the amplitude on a water wave, the air pressure in a sound wave

the square of that function y(x,t)2 ! ene"#y $e" unit

vo%ume, intensity (&) o' (aves is ene"#y density times (ave s$eed, so & y(x,t)2 ! can )e $ut do(n to num)e" o' $hotons (o" $seudo-$a"tic%es) at anyone $%ace at a ce"tain time, is a%so the %i*e%ihood o' 'indin# a $hoton (o" $seudo$a"tic%e) the"e (x) and then (t)

what we need is something altogether different but mathematically similar - a (ave e+uation 'o" matte" (ave, the so%utions to (hich, i.e. ,(x,t) the matte" (aves - (i%% )e a va%id desc"i$tion o'
1

ho( -sma%%. thin#s move and the s+ua"e o' (hich ,(x,t)2 (i%% #ive us the $"o)a)i%ity o' 'indin# the $a"tic%e o' the matte" (ave the"e (x) and then (t) ,(x,t) contains eve"ythin# that is and can )e *no( a)out the $a"tic%e, to #et the $"o)a)i%ity o' 'indin# the $a"tic%e at some s$eci'ic (x,t) (e have to ca%cu%ate ,(x,t)2 /o"n0s inte"$"etation
call the pro#a#ilit$ that particle will #e found in the infinitesi%al s%all interval d& a#out the point & '(&), pro#a#ilit$ densit$ as it is per length unit, then (orns interpretation is

1(x) dx = ,(x,t)2 dx (i%% )e a num)e" 2 3 (at ti%e t)

it is not $ossi)%e to s$eci'y (ith ce"tainty the $osition o' a $a"tic%e (x) - Heisenbergs uncertainty principle )ut it is $ossi)%e to assi#n de'initive va%ues o' $"o)a)i%ities 'o" o)se"vin# it at any $%ace (e ca"e to ca%cu%ate the s+ua"e 'unction 'o" (at a #iven time) )(&,t)2 is intensit$ of %atter wave, a %easura#le quantit$, while )(&,t) is onl$ a %athe%atical %odel for the %atter wave, a non ph$sical thing, cant #e %easured

Schrdingers equation equivalent to *ewtons second law, (Solutions to *ewtons second law descri#ed how things %ove at the %acroscopic scale+++ *ewton second law contained the solution of *ewtons first law, Schrdinger equation will contain equivalent to *ewtons firs law a free particle, plane wave, har%onic wave and superpositions of plane waves descri#ing a pulse)
Schrdinger developed his equation after his prior atte%pts to e&plain with de (roglies relation the (ohr %odel at a %ore funda%ental level failed, a colleague told hi% one does need a wave equation to %ake progress with waves, so Schrdinger #oned up on the %aths and found the one that works for all %atter waves +++

1a"tia% de"ivates and com$%ex num)e"s

suppose we have a function f(&,$) of two varia#les and want to know how this function varies with one varia#le onl$, sa$ & we treat the other varia#le $ as a constant and differentiate f(&,$) with respect to & result is called a partial derivate and written as
f df =, y =cons x dx

"u%es o' o"dina"y di''e"entiation a$$%y

.

e/g/ f = f(&,$) = $&2

f
2

f = y 2x x

as $ is a constant

on the other hand y = x as & is now a constant second order partial derivates repeating the procedure e/g/ f = f(&,$) = $& constant
2

2 f f = - , are 2 x x x

calculated #$

2 f = - y 2 x, = y 2 2 x x

as $ is again a

application on something more challenging

classical wave equation is
2 y 1 2 y = x 2 v 2 t 2

for electro%agnetic wave, sound wave, standing wave on a guitar, water wave, wave on a ver$ long string free to travel solutions of classical wave equation for %onochro%atic (0 = constant) unda%ped (1 = constant) wave traveling the right is $(&,t) = 1e-i0(t-&!v) now show that $ = 1e-i0(t-&!v) is a solution to the classical wave equation 'i"st $a"tia% derivate of $ with respect to &
y i = y x v

second derivate

2 y i 2 2 2 = y = y x 2 v2 v2

'i"st $a"tia% derivate with respect to t

y = i y t

second derivate

2 y = i 2 2 y = 2 y t 2

co%paring the second derivates, difference is 3ust the$ are identical so

2 y 1 2 y = x 2 v 2 t 2

1 v2

otherwise

which is the wave equation,

so $(&,t) = 1e-i0(t-&!v) %ust #e a solution to this equation

com$%ex (ave 'unctions / 4ust %i*e com$%ex num)e"s

) = 1 4 i(, then )5 = 1 6 i( , (i is replace ever$where #$ 6 i and one has the con3ugate co%ple& function) 1 real part of function ( i%aginar$ part

,2 = )5 ) = ) )5 = 12 6 i2 (2 = 12 4 (2

is all real i2 = -1
7

the 'undamenta% $"o)%em o' +uantum mechanics

#iven the (ave 'unction at some instant, say t = 0, i.e. ,(x,0), 'ind the (ave 'unction at some o" a%% othe" times t - (hen the"e a"e 'o"ces actin# on the $a"tic%e ,(x,0) is the initia% in'o"mation on the $a"tic%e, *ewtons %echanics analogue was initial position (&) and %o%entu% (p) of a classical particle, now it is an infinite set of nu%#ers a set of values, for all points & one value of ,(x,0) in *ewtons %echanics we o#tain&(t) and p(t) #$ solving *ewtons mdv second law F dt = dp, F = dt = ma , an net force acting on the particle changed its %o%entu%, change in position over kine%atics

5ch"6din#e"0s e+uation (57) $"o$a#ates ,(x,0)

'o"(a"d in time, that0s (hat (e (ant to *no(, #iven ((ithin 8eisen)e"#0s unce"tainty) (e *no( (he"e a $a"tic%e is and (hat its momentum the"e is, (e (ant to ca%cu%ate (e"e (i%% )e at some time (t) and (hat (i%% it0s momentum )e at that time
i/e/ the initial ,(x,0) chan#es into ,(x,t)
8

2 2 + U ( x ) = i 2 2m x t

9 = dx is the force acting on the particle :(&) is the potential energ$ function of the 9orce 1/ left hand side (;<S) of S= is first evaluated for )(&,>), i/e/ t = >, as it is not dependent on ti%e, i/e/ we %ake partial derivations and add the influence of the potential energ$ function on )(&,>) ;<S of S= equals right hand side (?<S) of S= result %ust #e equal to t at t = >, i/e/ initial rate of change of wave function 2/ fro% t at t = >, ?<S of S=, we co%pute )(&,dt), the wave function at an infitesi%al s%all ti%e interval (@t) later #$ superposition )(&,@t) = )(&,>) 4 t >

dU

, @t

./ that results gets plucked in at ;<S of S= again, #ut now we evaluate )(&,@t), i/e/ this ti%e %ake the partial derivations for )(&,@t) add the influence of the potential energ$ function on )(&,@t) (3ust like we did for t = >, first step), result is again equal to ?<S of S=

2/ fro% t at t = @t, ?<S of S=, we co%pute )(&,dt2), the wave function at an infitesi%al s%all ti%e interval (@t2) later #$ superposition )(&,@t2) = )(&, @t) 4 t @t

, @t2

BB each such repetition advances ) (&,@tn-1) one step in ti%e @tn forward until we have the ti%e (t C >) we want to investigate our particle again 6 it can all #e done #$ co%puter quickl$ and nu%ericall$ ---------------

Somebody could still asks: How does it work? What mechanism is represented by the wave unction? !obody has ever ound a mechanism behind the wave unction" !obody can e#plain more that we have $ust discussed" !obody will give you an e#planation about what is going on at a deeper level" %s a matter o act& we do not have an inkling about a basic mechanism rom which the wave unction could be derived"' R. P. Feynman, !"

nu%erical solutions of Schrdinger equations are fine #ut how %a$ one o#tain a %athe%atical e&pression for ,(x,t) %athe%atical procedure called separation of varia#les,

,(x,t) = ( x)(t ) =( x)e

i t

i' 9(x) $otentia% ene"#y is 'unction o' x on%y (not o' t) :::
d( t ) i = E(t ) dt
2 d 2 ( x ) + U ( x ) ( x ) = E ( x ) 2m dx 2

(ith 7 = h ' = 2 '=;

so ; =

(e can %oo* at the e-i;t 'acto" a)ove (hich desc"i)es the time de$endency i' the $otentia% ene"#y does not de$end on time so that time de$endency 'acto" is e in equations a#ove, = is the total energ$, which we can nor%aliEe to #e the kinetic energ$ plus the potential energ$, (if we set rest energ$ =>= >, as a reference for% which energ$ is counted - which we can do ar#itraril$)
d 2 ( x ) 2m + 2 GE U ( x )F ( x) = > dx 2

iE t

rearranged for further use and called, ti%e independent, stead$state, or stationar$ Schrdinger equation in one di%ensions if we have an ar#itrar$ potential energ$ function :(&) there are no e&plicit anal$tical solutions to this equation

must )e -(e%% )ehaved. 4ust as , has to in

order to give sensi#le results for pro#a#ilities, i/e/ finite ever$where including 4- , single valued for an$ &, continuous, and Is%oothJ 6 which is dx %ust also #e continuous and single valued (the Serwa$ #ook sa$s hereK wherever :(&) has a finite value, other #ooks sa$ all the ti%e)
d

a%% o' them a"e mathematica% conditions, so ca%%ed )ounda"y conditions

i' (e can se$a"ate the va"ia)%es, (e a%so #et ,(x,t)2 = , %eaning all pro#a#ilities we calculate fro% ,(x,t) (i%% not de$end on time, a"e static o" stationa"y
2

ex$ansion to th"ee dimensions st"ai#ht'o"(a"d

1>

 2 ( x, y , # ) + dx 2 2 ( x, y , # ) + dy 2 2 ( x, y , # ) + d# 2 2m GE U ( x, y , # )F ( x, y , # ) = > 2

conse+uence at %east < +uantum num)e"s, ta*in# account o' the s$in o' the e%ect"on it (i%% )e = 'o" e%ect"ons con'ined to )e in an atom

%et0s %oo* at a '"ee $a"tic%e in the $%ane (ave a$$"oximation, a%so ca%%ed a ha"monic (ave
free non-relativistic particle %eans no force on it 9 = > = dt , no force %eans no potential energ$ :(&), and no dependence of the potential energ$ on t, as particle is free, all energ$ is kinetic = = L% v2 one di%ensional ti%e independent S= si%plifies to
d 2 ( x ) 2m mv 2 +- 2 G F, ( x ) = > dx 2 2
dU

L% v2 can #e rewritten as
) , #racket $ields - (
2

p2 2m

, %ultipl$ing within the straight

p = h! and nu%#er

h 2

so

p 2 )

= (2M! )2 = k2 per definition of wave

11

d 2 ( x) 2 + $ ( x) = > NN for N a N free N particle 2 dx

( x ) = ei$x ( x ) = %ei$x ( x ) = e i$x ( x ) = &e i$x
( x ) = %ei$x + &e i$x

%ost general

are all solution of one di%ensional ti%e independent Schrdinger equation, where 1 and ( are ar#itrar$ constants (such constants appear generall$ in solutions to the S= and we will define then in the nor%aliEation process) we had

,(x,t) = ( x)(t ) =( x)e

i t

so in order to get %ost general solution of ti%e dependent S=

,(x,t) (e mu%ti$%y most #ene"a% time inde$endent so%ution ( x ) (ith time de$endence e
i t

,(x,t) =

( %e i$x + &e i$x )e it

%ei$x it + &e i$x it = %e i ( $x t ) + &e i ( $x t )

where is that ree particle? answerK calculate ,(x,t)2

re%e%#er an$ function (#e it e&ponential or sinusoidal) of fro% (k& O 0t) represents a traveling wave

12

for (k& - 0t) wave is traveling to the right for (k& 40t) wave is traveling to the left, lets decide our particle should travel to the right, we can do that #$ setting ( = > in the %ost general solution 2 so ,(x,t) = ,> , = %e %e = % e = % 1
i ( $x t ) i ( $x t ) 2 > 2

so the pro#a#ilit$ is a constant 12 = ,0(x,t) at all places and ti%es we %a$ have as well calculated ( x ) to find the pro#a#ilit$ of finding the particle for an$ & we want
2

( x ) 2

= ( x)
5

( x)

%e i$x %ei ( $x ) = %2 e> = %2 1

1.

anal$Eing the graph we see that the pro#a#ilit$ of finding the particle in an$ one seg%ent of equal length P& or d& is a#solutel$ the sa%e as it is a constant, so the particle has equal pro#a#ilities to #e at an$ place, there is no %ost likel$ place so lets assu%e we have a '"ee $a"tic%e movin# to the "i#ht, e&pressed #$ wave function, see what happens if we put it into Schrdinger
equation

,(x,t) =

%e i ( $x t ) = %-cos $x t ) + i sin( $x t ),

where 1 is a constant, lets differentiate partiall$ for & and t and put our derivates into the ti%e dependent (one di%ensional) Schrdinger equation
= i%e i ( $x t ) = i t

2 = (i$ )2 %ei ( $x t ) = $ 2 x 2

as it is a free particle, it is not under the influence of a force, so it has constant (ti%e and position independent) net potential energ$ :(&) = :>, which %a$ #e Eero or an$ other value (re%e%#er potential energ$ levels can #e set ar#itraril$)

2 2 + U ( x ) = i 2 2m x t

plugging our derivates in

12

2 ( $ 2 ) +U > = i ( i) 2m

which we can divide #$ )+++

and we get
2 2 $ +U > = 2m

as we know so what is
2 2 $ 2m

= E total = 'E + PE

2 2 $ 2m

with k2 = (2M ! )2 and p2 = (h ! )2 = %2v2 is kinetic energ$ of the free particle %oving

= L % v2

to the right

()*& ormalism makes sense

as %on# as the"e is no net 'o"ce, a $a"tic%e does not chan#e momentum, and moves in a st"ai#ht %ine at constant s$eed, uni'o"m %inea" motion 4ust the same 'o" mac"osco$ic $a"tic%es is stated in ?e(ton0s 'i"st %a(,
?e(ton0s 'i"st %a( is contained in, i.e. it is actua%%y a so%ution o' ?e(ton0s second %a(, 4ust as ha"monic ($%ane) (ave is a so%ution o', i.e. is (contained in), 5ch"6din#e"0s %a(

'"ee $a"tic%e so%ution can a%so )e ("itten as

,(x,t) =

%e i ( $x t ) = %-cos $x t ) + i sin( $x t ),
2 p

(ith 7 = h ' = 2 ' and = h /$ =

17

,(x,t) =
%e
i ( 2 x 2 ft )

= %e

x i 2 ( ft )

= %e

i 2 (

E p t x) 2 2

= %e

i ( Et px )

where = =

p2 +U ( x , t ) 2m

Q= 4 '=

@et0s %oo* a#ain at $"o)a)i%ity density, no"ma%iAation and )ounda"y conditions normali+ation: '(&) d& = )(&,t)2 d&
is pro#a#ilit$ that particle will #e found in infinitesi%al interval d& a#out the point &, '(&) is called pro#a#ilit$ densit$ (here in %-1also %-2 or %-.

as pro#a#ilit$ has to #e a single value at ever$ (&) point we care to look at to %ake sense, )(&,t) and )(&,t)2 have to
#e single valued and continuous functions (of & and t) to %ake sense, in addition, the$ have to #e s%ooth

general solutions to the Schrdinger equation contain ar#itrar$ constants which we can ar#itraril$ assign values

18

to, so a good idea is to use these constants for nor%aliEation procedures Rf we know the particle %ust #e so%ewhere (within so%e length, or area, or volu%e for which we have precise values, e/g/ &1 and &2 (&1 S &2 ) or even infinite values 4- we specif$ the ar#itrar$ constant so that %eaning the particle does e&ist #etween &1 and &2 with 1>> T certaint$ at all ti%es

x1 x2

( x, t ) 2 dx = 1 = 1>>T

an$ wave function which satisfied this conditions is said to #e nor%aliEed )(&,t) if we have such a nor%aliEed )(&,t), we can calculate the pro#a#ilit$ of the particles e&istence #etween a and #, where a U &1 and # V &2 in T #$ so if we forget to nor%aliEe we have 3ust ' W pro#a#ilit$ of finding the particle there and then, with nor%aliEation this #eco%es a %easure in T
P = ( x , t ) 2 dx
a b

in all cases ' is 3ust the area under a curve

1A

this sets a strict condition to ) if it is not onl$ to #e a function that happens to solve the Schrdinger equation, #ut also to represent the pilot!guiding!%atter wave of a real particle the a"ea unde" the cu"ve has to )e 'inite so that it can nor%aliEed to #e 1 or 1>> T, so )(&,t) has to go to Eero for &1 and &2 otherwise )(&,t)2 would not go to Eero and the area under the curve would not #e finite

1D

exam$%eB /oh" "adius in hyd"o#en atom

boundary conditions must )e 'u%'i%%ed 'o" ,(x,t) to "e$"esent a "ea% $a"tic%e

1H

well behaved unctions

) and %ust #e Iwell #ehavedJ in order to give sensi#le results for pro#a#ilities, i/e/ finite ever$where, single valued for an$ & (and t), continuous, i/e/ having & (and t) values ever$where (unless X(&) is infinite) and Is%oothJ 6 which is dx %ust also #e continuous wherever :(&) has a finite value in addition to #eing a solution of the Schrdinger equation so boundary conditions and re,uirements o normali+ation will %ake it possi#le for us to decide (hich so%ution o' 5ch"6din#e" e+uation "e$"esent "ea% $a"tic%es and which are a purel$ %athe%atical construct
d

2>

exam$%e '"ee -$a"tic%e.

note that the solution of the Schrdinger equation that descri#es this particle can not #e (easil$) nor%aliEed, as the area under the parallel line reaching fro% 6 to 4 infinit$ is infinite+++, that& however& was implied by the de inition above

so this wave function does not descri#e a Ireal ph$sicalJ particle, it is however a ver$ useful starting %odel for a real particle as we can construct for% such waves #$ %eans of superposition an accepta#le %odel for a real particle, 3ust as we did for electro%agnetic waves in chapter 2

that real particle will then have a wave function that can #e nor%aliEed and the plot of it pro#a#ilit$ densit$ function will show a pulse with has finite values at so%e region x , peaking so%ewhere, and going to Eero ever$where else, especiall$ when & approaches 4- infinit$ %et0s %oo* at the unce"tainty $"inci$%e a#ain,
21

 x p x 2

and appl$ it to the free particle in the graph a#ove if the particle is free, no net force acts on it, *ewtons 1st law states, if there is no net force acting, there is no change in %o%entu%, so which a%ounts to a violation of the uncertaint$ principle, a %odel can violate the principle, #ut not a real particle, so the free particle descri#ed #$ one plane wave function (rather that a su% of %an$ plane wave functions) is not a real particle
p x = >

havin# a '"ee $a"tic%e desc"i)ed )y a $u%se (i%% a#ain mean (e have mathematica% unce"tainties
P& Pk Y 1 P0 Pt Y 1 in the %odel that translate to real ph$sical uncertainties when we %ake a ph$sical interpretation of the %odel #$ replacing Pk 2 2p with = h (after de (roglie) and %ultipl$ing #oth sides with
=

(analogousl$K appl$ing the definition of 0 = 2M f and = = h f ('lank-=instein equation) gives ph$sical %eaning to P0 Pt Y 1)

h 2

22

so we dont violate with the %athe%atical %odel for the pulse!wave #undle!wave packet <eisen#ergs uncertaint$ principle and this descri#es a real particle, in addition, the area under a pulse will of course #e finite, so we can nor%aliEe our wave function

7x$ectation va%ues and C$e"ato"s

the solutions to the Schrdinger equation contain ever$thing that can #e known (i/e/ which the uncertaint$ principle allows us to know) a#out the %ove%ent of an entit$ that is a wave-particle with %ass so lets e&tract the (arith%etic) %ean position 6 which is also called the e&pectation value, ($our #ook states here incorrectl$ the average position, an average does not refer to a distri#ution!population #ut the arith%etic %ean does), 1 x = f x n
n i i i =1

where f is the di%ensionless frequenc$ of occurrence of one particular value of & (forget a#out p 217 lower half and p 218 top paragraph, R a% prett$ sure that is incorrect as R did not find a si%ilar Zodern 'h$sics treat%ent in (eiser and "ipler

short maths into

2.

if the Isa%ple of & valuesJ is large the %ean of these values %a$ #e taken as an esti%ate of the distri#ution!population %ean the su% of all discrepancies for% the %ean is Eero

( x
i =1

x) = >

the va"iance o' the mean

s2 = 1 n f i ( xi x )2 n 1 i =1

for large n, one can appro&i%ate n with n-- and use the variance of the population
var( x ) = 1 n 1 n 2 f ( x ) f i ( xi ) 2 as i i n i =1 n 1 i =1

a %easure of variance of

the sa%ple standard deviation ([) is the square root of the variance and another %easure of the a%ount of scatter in the data if [ = > then var(&) = >, there is no spread in the data and the distri#ution is called sharp the uncertainl$ principle now tells us that particle positions (&) can onl$ #een know with pro#a#ilities, i/e/ its distri#ution is never sharp and alwa$s fuEE$

22

)ac* to the ex$ectation va%ue, DxE

<x > = x ( x, t ) 5 ( x, t )dx

where )(&,t) has to #e nor%aliEed

de'inition the arith%etic %ean of & that would #e e&pected fro% %easure%ents of the positions of a large nu%#er of particles with the sa%e wave function+
dont confuse with pro#a#ilit$ of finding a particle in an infinitesi%al interval around & 6 its co%pletel$ different things, so ' = > %a$ #e co%pati#le with a finite e&pectation value S&C e/g/ for an infinite square well and even quantu% nu%#er wave functionsK '(;!2) = >, #ut S&C = ;!2 #ecause )2 and also 2 are s$%%etric a#out that point to calculate we have the definition of the e&pectation value S&C
<x > = x ( x ) 5 ( x )dx

we need nor%aliEed wave functions, and the$ are

n =
2 nx sin , NNNNNNNN n = 1,2,.,/// ( (

as there is no i(s) 1 , the con3ugate co%ple& function has the sa%e for% and the 2 are si%pl$
n2 =
2 nx sin 2 , NNNNNNNN n = 1,2,.,/// ( (

27

so the integral #eco%es

<x > = x( x ) 5( x )dx =

2 (

>

x (sin

n x n x )(sin )dx ( (

< x >=

2 nx 2 x x sin 2 dx = - > ( ( ( 2
( 2

x sin(

2nx 2nx ) cos( ) ( ( ,( > 2 n n D( ) 2 ( (

since sin (nM) = >, cos (2nM) = 1 and cos > = 1, for all values of n the e&pectation value of & is
< x >= 2 (2 ( ( )= ( 2 2

in all quantu% states, the arith%etic %ean position of the particle is in the %iddle of the #o& for n = 2,2,8 the IaverageJ position is also ;!2 and this has nothing to do with = > the pro#a#ilit$ densit$ of finding the particle there
2

28

no( the ex$ectation va%ue o' any 'unction o' x can )e ca%cu%ated the same (ay
< f ( x) > = f ( x ) ( x, t ) 5 ( x, t )dx

so f(&) can #e potential energ$ :(&) for e&a%ple however no function p = p(&) e&ist #$ virtue of the uncertaint$ principle, Pp& P& U 2 if #oth of these entities var$ in a fuEE$ wa$ there si%pl$ cant #e a relation #etween the two of the% (there is si%pl$ no classical path in quantu% %echanics)

$ = mv )ut $ F $(x) in +uantum mechanics

2A

there is the sa%e pro#le% with e&pectation value of =, a there is an uncertaint$ principle as well P= Pt U 2 onl$ if we are considering a stationar$ state, i/e/ when there is no ti%e dependenc$ and no Pt, no such uncertaint$, we will have sharp values for energ$

so (hat (e need he"e a"e o$e"ato"s

operator is a %athe%atical concept telling us what to do with the operand that follows it e/g/ ( i x ) (&2 t) %eans that one has to take the partial & derivate of the function (&2 t) and %ultipl$ it with i so
( ) i x

(&2 t) =
) i x

2 xt i

what is

(cos & ) = - ( i ) sin &

entities for which we have operators are called o#serva#les as the$ have ph$sical %eaning and can #e o#served (although su#3ect to the uncertaint$ principle)

no( ( i x ) is actua%%y the momentum o$e"ato" G$H that #ives us the ex$ectation va%ue o' the momentum D$E

note that the order of factors is i%portant, there is onl$ one wa$ of doing it correctl$
<p > = ( x, t ) 5

( x , t )dx i x

2D

si%ilarl$
<p2 > = ( x, t ) 5

G ( x, t )Fdx i x i x

'i"st one o$e"ato" is a$$%ied to its o$e"and yie%din# the o$e"and 'o" the second o$e"ato" (which will again stand to
the right of the operator) or e#ample: calculate the e&pectation value SpC for the ground state wave function in the infinite square well, we know it is a stationar$ state (standing wave) so it is ti%e independent, we know the particle is trapped in the well, so it is never outside, so we can restrict the integral to the well the (nor%aliEed and ti%e independent) wave function for that 2 x state is = ( sin ( as there are no i(s) in it the con3ugate co%ple& of that functions 5 is also
2 x sin ( (

so

< p >=
>

2 x 2 x sin( )( ) sin( )dx ( ( i x ( (

2 x x sin( ) cos( )dx = > i ((> ( (
(

si%plifies to

< p >=

this is of course #ecause sin & = > at the nodes++

2H

so the e&pectation value SpC is Eero, what does it %ean, si%pl$ the particle is 3ust as likel$ %oving to the right as it is %oving to the left, the arith%etic %ean %ust, thus, give Eero generall$ operators are written in sharp straight #rackets, i/e/ -p, \ or with a IcaretJ, i/e/ p as there are %an$ %ore o#serva#les, entities with ph$sical %eaning that are allowed to #e known #$ the uncertaint$ principle, there are %an$ %ore operators that give us e&pectation values of these o#serva#les total energ$ operator -=, =
i t

kinetic energ$ operator non relativistic

2 < p > 2 1 2 2 = ( ) = -Q=, = 2m 2m i x 2m x 2

'otential energ$ operator -('=), = -:, = :(&) now lets see if ever$thing is consistent with the Schrdinger equation = = Q= 4 : so we %ust also have
2 2 i = +U t 2m x

-=, = -Q=, 4-:,

that is equivalent to

now we %ultipl$ #oth sides with as these Igu$sJ are operators)

(it

has to co%e fro% the left

.>

and get

2 2 i = +U ( x ) t 2m x 2

so postulating #oth -=, = -p,= i

i t

is equivalent to postulating the Schrdinger equation +++ now notice the operators of kinetic and potential energ$ are onl$ involving spatial coordinate &, we can define a co%#ined operator for the total energ$ that also involves onl$ the spatial coordinate &, this is call the <a%iltonian operator -<, -<, =

2 2 +U 2m x 2

su% of kinetic and potential energ$ operator %ust also #e total energ$ operator that involves onl$ ti%e coordinate (t) ==
i t

so we have actuall$ two total energ$ operators and if the$ operate on the sa%e wave function, the %ust $ield the sa%e o#serva#le e&pectation value ++ again %ultipl$ing with $ields

-<, = -=,
.1

the Iprett$ co%pactJ version of the Schrdinger equation

)igenvalues and )igen unctions

for si%plicit$ we deal here onl$ with ti%e independent wave functions, if so%ething is in a stead$ state the uncertaint$ principle P= Pt U 2 does not appl$, there is all the ti%e in the world, so the energ$ has settled into a stationar$ state an e&act value, it is onl$ when it 3u%ps #etween stationar$ states that there is a Pt again, and with it an uncertaint$ of energ$ that shows up in a widths of a spectral line IeigenJ is ]er%an and %eans self, so what is %eant here is co%#inations of real nu%#ers (values) and functions that are equivalent to the action of an operator on these functions/
(if $ou know a#out s$ste%s of linear equations and %atri& representation, $ou have the ver$ sa%e things, co%#inations of vectors with values that are IselfJ solutions to the pro#le%, was invented in ]ttingen #$ ^ordan and <il#ert, who told (orn und <eisen#erg a#out it, B)

%athe%atical definition -],)n = gn)n where d e/g/ operator dx has eigen function = e what is the eigenvalue to this functions and operator
2
2x

d 2 2x d d 2x d e = ( e )= 2e 2 x = 2e 2 x 2 dx dx dx dx

as the eigen function was 3ust e the (generall$ real) nu%#er 2 is d for that function e&actl$ equivalent to the operator dx
2x

.2

back to physics
eigenfuctions are here again solutions to the Schrdinger equation, we deal onl$ with ti%e independent for% if we are looking at stationar$ states such as in the case of a particle in a #o& we get sharp values for certain operators such as the total energ$ operator, so there is no e&pectation value for energ$ as there is no arith%etic %ean of %easure%ents on %an$ identical particles, if we are dealing with an eigenvalue!eigenvector pro#le% the eigenvalue is 3ust one value, e/g/ a definitive energ$ for ever$ eigenfunction, , eigenfunction and eigenvectors are refereeing to a set of quantu% nu%#ers that are integers from particle in an infinite square well, you $now&
n

energy comes only in discrete values& =n, these are the eigenvalues to the eigen unctions
so time inde$endent 5ch"6din#e" e+uation can )e ("itten most com$act%y

-<, = =n
n

or correct description o atoms we will have a second set o eigenvalues and eigen uctions& because angular momentum is in nature also ,uanti+ed not only energy& so there will be another ,uantum number actually there will be two more sets
of eigenfunctions and eigenvalues as a state of an electron in an atom is described by ) quantum numbers

..

.odel: 1a"tic%e in a )ox (ith in'inite%y %a"#e $otentia% )a""ie"s, in'inite s+ua"e (e%%
in inite barriers& the particle is always con ined& never outside e&erciseK deriving for% of the wave function under the #oundar$ conditions its a stationar$ state, so we use ti%e independent Schrdinger equation
d 2 ( x ) 2m + 2 GE U ( x )F ( x) = > dx 2

so ( x ) = > outside the #o& inside #o& :(&) = >

d 2 ( x ) 2mE ( x ) d 2 ( x ) + = > = + $ 2 ( x ) 2 dx 2 dx 2

solutions of this ordinar$ partial equation are sin k& and cos k& so %ost general solution is
( x ) = % sin $x + & cos $x

inside the #o& > S & S;

ho( a)out x = 0 = @I
.2

well interior wave %ust %atch e&terior wave to #e continuous d ever$where, #ut the slope dx is not continuous, so it is not a real ph$sical situation, 3ust a %odel that %a$ appro&i%ate a real ph$sical situation prett$ well so interior wave %ust vanish at & and ; we can o#tain this #$ setting
(>) = & = > NNN for N x = >

so the cosine her% is gone this requires k;=nM where n is 1,2,., B

( () = % sin $( = > NNN for N x = (

#ecause k = 2M! this is equivalent to fitting an integer nu%#er of half-wave length into the #o& using k

= nM!;

and re%e%#ering that

d 2 ( x ) 2mE ( x ) d 2 ( x ) + = > = + $ 2 ( x ) (as 2 2 2 dx dx

ou" sta"tin# $oint

we find that the particles energ$ is quantiEed

En =
2 2 $ n 2h 2 = 2m Dm(2

4ust the same "esu%t as (e o)tained in Jha$te" = '"om nodes o' standin# (ave conditions
.7

looking at ( x ) there are places #esides the walls (& and ;) where the particle can never #e found+++
n> 1 2

for ( x ) the particle is never at 1!2 ; for ( x ) the particle is never at 1!. and 2!. ;
2 2
2 .

how does the particle get over these points ___ well its particle-wave dualit$ not 3ust a particle of which we have an intuitive idea how it is supposed to %ove 6 so%ething we cant grasp with or #rain having evolved over ti%e looking onl$ at classical
.8

pheno%ena 6 and of course, there is no path the wave-particle could follow

so far we onl$ looked at ( x ) to %ake calculations of actual pro#a#ilities, we need to nor%aliEe the wave functions
2 n

P = ( x ) 2 dx = 1 = % 2 sin 2 (
> >

nx )dx (

there is a trigono%etric identit$K 2 sin2 ` = 1 6 cos2` so we get

1 = %2 sin 2 (
> (

nx 1 ( 2nx )dx = %2 1 cos( )dx > ( 2 ( 2 x (

now cos &=;

( >

integrates to

sin

2 x (

which is Eero at & = > and

1 dx is 3ust ; 6 > = ;

so 1 = 1=
2 (

%2 ( 2

fro% which we get the nor%aliEation factor

our wave functions read$ to #e evaluated for pro#a#ilit$ densities in T are, thus,
n ( x ) =
2 nx sin( ) ( (

with n = 1, 2, ., B

.A

one mo"e thin# on the in'inite s+ua"e (e%%

the lowest energ$ state is given #$ n = 1 what would happen is n = > _
d 2 ( x ) => dx 2

is to )e so%ved :

solution is wave function

(inside N box ) = %x + &

this wave function has to #e Eero at & and ;, this requires #oth 1 and ( to #e Eero
(inside N box ) = %x + & = > N everywhere+++

is we look at the pro#a#ilit$ of finding this particle

( >

( x, t )2 dx = > = >T = there N is N no N such N particle

so n = > and = = > are not possi#le +++ returning to wave function for particle in infinitel$ deep #o& ! infinite square well
n ( x ) = % sin
nx (

.D

for each of the quantu% nu%#ers, 1, 2, ., B there is a specific wave function descri#ing ever$thing that is per%itted to #e known #$ the uncertaint$ principle

one %ast thin# on the in'inite s+ua"e (e%% with assu%ing i%penetra#le walls of infinite height, we actuall$ violated one of the #oundar$ conditions for ph$sical %eaningful wave functionsK derivates of wave function with respect to space ( x ) d ( x, t ) coordinates (&,$,E), i/e/ x or x = dx %ust #e continuous, this %eans slopes %ust #e continuous in the infinite square well %odel, the wave functions 3ust Ikind of stoppedJ at the walls, analogous to a classical wave on a string of a guitar, that would stop and get reflected #ack %aking up the standing wave 6 %aking %usic /// #ut the real world is different on a quantu% level, if it is to #e a real particle that is represented #$ a solution to the Schrdinger equation, the slope has to #e continuous, so a real particle-wave does not stop at an$ #arrier, it alwa$s IleaksJ into the #arrier, and if the #arrier is not infinitel$ thick (which it never reall$ is in the real world either) the particle has a
.H

pro#a#ilit$ to #e found outside the well, when it has ItunneledJ through the #arrier (as it didnt have enough energ$ to go over the top of the wall)
so lets sum up:

in nature, there are no infinite potentials ene"#y

(a%%s, so we should consider an alternative %odel,

inite s,uare well& particle in a bo# with inite wall heights

(of either infinite thickness or finite thickness, again there are no walls of infinite thickness, #ut we %odif$ our %odel one thing at a ti%e )

2>

if it has sufficient kinetic energ$, classical particle can go over the top of a finite wall and %ove freel$ outside, #ut with reduced speed corresponding to the di%inished total energ$ kinetic energ$ Q= = =-'== =-: C > #ut if total = is s%aller than the height of the potential energ$ walls of the well, i/e/ =-'= = =-: S >, there is no kinetic energ$ left to roa% freel$, so classical particle cant #e outside the wall and %oving, it is trapped forever in > S & S ;

&n +uantum mechanics, )ecause o' the condition o" x = dx must )e continuous, i.e. s%o$es must )e continuous,
21
( x, t ) x ( x ) d

a $a"tic%e %ea*s out into the $otentia% (a%%s +++ "his is #ecause ) is never Eero outside the well, so the pro#a#ilit$ of finding the particle there )2 is not Eero either, so the particle is actuall$ there +++ so lets look at the parts of the wave function that penetrated into potential walls
solutions to the (ti%e independent) Schrdinger equation
* ( x ) = +ex

for & S >, section R, where a is a constant we can use for fit to the second seg%ent for & C ;, section RRR, where b is a constant we can use for fit to the second seg%ent is a positive constant, as : is taken to #e Eero

*** ( x ) = ,ex

and =

in the well and so%e positive value outside the well

2m(U E ) 2

so (e have an ex$onentia% decay, thats pretty ast&

fro% of the constant c, we can see that the heavier the particle is and!or the larger the difference : 6 =, (i/e/ the larger 6 Q= of the #ound state) the faster ( x ) deca$s in the walls, if the walls are infinitel$ wide, the wave function deca$s to Eero

22

general solution for region RR is

** ( x ) = % sin
2mE x + & cos 2mE x

as :(&) = > in the well

and k = as usual #ut as sin (>) = > we have to set 1 = > and can onl$ use the second part with IcosJ functions that IcosJ function has to %atch with the functions for section R and RRR at & = > and ; and its first derivate with respect to & has to %atch as well (s%oothness condition of wave functions that descri#es real particles) for & = > and ; this can onl$ #e achieved for certain energ$ levels =n which are all s%aller that their counterparts fro% the infinite square well of the sa%e widths
En
inf inite N square N well

2mE

2 2 $ n2h2 = 2m Dm(2

e&a%ple sa$ we have n = 1 and ( () = 2 , i/e/ at the wall is onl$ half the %a&i%al value of this function at the center
%a& ** **

**

so we can sa$ cos k; = 1!2 k; = 8>d = M!. k = M!.;

E1
finite N square N well

k=
=
2 2 12 h 2 = 1Dm(2 1Dm(2

2mE1

fro% a#ove, resolved for =1

2.

or that particular scenario e&actl$ 2/27 ti%es s%aller

due to the particular height and widths of the square potential well, i/e/ : and ;, that results in the value of the wave function at ; 3ust #eing half the %a&i%u% value (which we have in the center of the well) on can also see for% the graph that the wavelength that fit into a finite square well (with leakage into the #arriers) are so%ewhat larger than those wavelength that would fit into an infinite square well of the sa%e widths, larger wavelength correspond after de (roglie ( = h ! p) to s%aller %o%enta (p), and %o%enta p are liked to kinetic energ$ #$ Q= = 2m
2

the similarity between inite and in inite s,uare well is also e&pressed in the concept of a penetration depth @
per definition
=
1

2m(U E )

at a distance @ #e$ond each of the well edges the a%plitude of the wave function has fallen to 1!e of its value at the edges, and approached Eero e&ponentiall$, i/e/ ver$ ver$ fast #e$ond @ with that we can %ake an appro&i%ation
En
finite N square N well

2 n 2 2 2m( ( + 2 ) 2

(which shall #e sufficientl$ accurate if @ SS ;)

22

which effectivel$ sa$s that the widths of the well is Ie&tendedJ #$ O @, i/e/ a total of 2 @, and we have the sa%e relation to calculate the energ$ levels as we had #efore for the infinite square well now @ is dependent on =, see relation a#ove, so solving for finite N square N well En #$ this appro&i%ation will #e an iterative process

27

semiconducto" +uantum dots- at last the real thing

trap for an electron and a hole in a se%iconductor is realiEed #$ e%#edding a se%iconductor entit$ of the order of %agnitude 1> n% dia%eter and with a s%aller #and gap into a se%iconductor %atri& with a larger #and gap particle in these IwellsJ is #ound state of an electron and a hole, if free its called an e&citon, if it is trapped its called an e&citonic polaron usual quantu% %echanical treat%ent with Schrdinger equation, B applies, as a ver$ crude appro&i%ation it is a three-di%ensional square #o& with finite (height and thickness) potential energ$ walls, the %atter wave leaks into the #arrier and to so%e e&tend tunnels through it, otherwise a device could not work its also called a pseudo-ato% as there are discrete energ$ level, so there is the analogue of spectral lines

quantu% dots such as this %a$ #e used in future for new co%puter architectures such as quantu% 28 cellular auto%ata

deposition, surface diffusion, interdiffusion are rando% events, s%aller #and gap se%iconductor (allo$) usuall$ larger lattice constant, -one way of self. assembly, resulting in /ca$e with raisins01

epita&iall$ grown quantu% dots co%pressivel$ strained and possess rando% distri#ution of ato%s e ordinarily strained (*s

2A

ove" time, atomic o"de"in# as o)se"ved )y t"ansmission e%ect"on mic"osco$y

a

5 nm

5 nm

Ki#u"e 3B (Rn,]a)S# agglo%erates in ]aS# %atri&f (a) ->>1, plan-view <?"=Z i%age which was recorded at 7>> ga and after a ther%al treat%ent in the electron %icroscope at te%peratures of the order of %agnitude of the growth te%perature for several hours, ref/ 12, suggesting that the transfor%ed structure of this hb rather than its original sphalerite protot$pe structure is ther%od$na%icall$ sta#lef ()) S11>C cross section i-contrast S"=Z i%age, showing a hb with ato%ic ordering in ever$ forth O (>>2) planef power spectra as insertsf c) ->>1, ato%ic resolution i-contrast S"=Z i%ages of structurall$ transfor%ed Rn(1s,S#) hbs in Rn1s %atri&/

(fro% one of %$ papers, see we# pages, if interested)

'S:s new %ore than j 1,>>>,>>> %icroscope, would itself not #e possi#le without %odern ph$sics and Schrdingers equation, #ecause design of electro%agnetic lenses is quite involved, ra$ optics does not do the 3o#, its too crude an appro&i%ation

2D

(uantum states o Harmonic /scillator& a very use ul appro#imation

sa$ a particle is in potential well su#3ect to a linear restoring force F = ' x with force constant Q corresponding potential energ$ is :(&) = L Q &2 we had so%ething like it as a %ass on a spring, a ver$ long pendulu% with a s%all elongation, B/ an$thing that is li%ited to s%all e&cursions (&) around a sta#le equili#riu% position
near the sta#le equili#riu% position, sa$ & = a, the potential energ$ can #e appro&i%ated #$ a para#olaK :(&) = :(a) 4 LQ(&-a)2 under the condition that the curvature of that para#le %ust %atch that of :(&) at the point & = a, this condition is fulfilled if Q=
d 2U dx 2

ka

and :(a) is potential energ$ in equili#riu% position a, which we can of course define as the Eero level fro% which all potential energies are %easured, analogousl$ we can use coordinate shift and define a = > on the & a&is with these two conventions we have

:(&) = :(a) 4 LQ(&-a)2 = > 4 LQ(&->)2 = LQ &2

2H

in other words, a particle that is li%ited to s%all enough e&cursions a#out a sta#le equili#riu% position appro&i%atel$ #ehaves as if it were attached to a string with a force constant prescri#ed #$ the curvature of the true potential at equili#riu%

now if the oscillation is si%ple har%onic (as in classical ph$sics), with angular frequenc$ = ' (dont confuse Q - the m force constant with k the wave nu%#er) and we can write for the potential energ$

:(&) = LQ &2 = L % 02 &2

and put this potential energ$ function into the ti%e independent Schrdinger equation
d 2 ( x ) 2m 1 = 2 ( m 2 x 2 E ) ( x ) dx 2 2

as we are interested in the stationar$ states of the s$ste%

the kind of wave functions we had so far in this chapter are all for constant potential energ$ function, either Eero or so%e finite value for all &, here the potential energ$ is a function of &2

7>

ground state, n = >, note is a %athe%atical

consequence

and => = L = L h f (also called Eero point energ$, as it is for n = > lowest quantu%
nu%#er

=1= .!2 h f, =2= 7!2 h f , =n = (n 4 1!2) h f, n = >, 1, 2, . so P= = hf or so%e %ultiple of hf, 'lanck was right in his 1H>1 paper +++
-L 2 x 2 L a"e the %imits a c%assica% osci%%ato" (ou%d have, in a sense these li%its are #arriers of the potential well, and there is a Ilot of leakageJ into these #arriers,
so in a classical picture the string would get overstretch so severel$ that it %a$ not spring #ack

note that even a classical oscillator does have a Eero point energ$ = L h f

because things never stand still in nature

71

that leakage into the #arriers is shown #elow as well for so the particle is actuall$ at these positions with certain pro#a#ilities
2 n

for large quantu% nu%#ers classical ph$sics (dashed lines) and quantu% ph$sics (curves) give corresponding pro#a#ilities of finding the particle

72

T"ansitions )et(een states and se%ection "u%es

energ$ levels revealed when s$ste% %akes transitions, either to a higher energ$ state as a result of e&citation (a#sorption of energ$) or to a lower energ$ state as a result of rela&ation (de-e&citation, e%ission of energ$ , if it is an electron this is usuall$ electro%agnetic radiation)

'o"m c%assica% $hysicsB if a charge q is accelerated, it

radiated electro%agnetic radiation, re%e%#er thats how l-ra$s are produced, if a charge oscillates, the radiation is of the sa%e frequenc$ as the oscillation if we have charged particle (charge q), we define charge densit$
n = q n 5 n

this quantit$ is ti%e independent, stationar$ state, i/e/ does not radiate, quantu% %echanical e&planation of (ohrs postulate, lets sa$ n is the ground state
n

with this wave function goes a certain (eigen-value) energ$ =n , as long as the charged particle is in this energ$ state it does not radiate, it does neither lose nor gain energ$ sa$ it gained 3ust the right a%ount of energ$ to go to an e&cited state, this %eans eigen-value (energ$) and wave function eigenfunction change
7.

lets now consider how the particle returns to the ground state onl$ if a transition for% one wave function (%) to another wave function (n) is %ade, the energ$ changes P= = =% 6=n fro% one definitive value (e&cited stationar$ state, e/g/ %) to the other definitive value (rela&ed stationar$ state, e/g/ n), =% C =n as wave function for a particle that can %ake a transition, we need ti%e dependent wave function )(&,t), as it is two different states % and n, we have a superposition )%,n(&,t) = a )%(&,t) 4 # )n(&,t) initiall$ sa$ a = 1, # = >, electron in e&cited state, % while in transition a S 1, # S1, electron is oscillating #etween states finall$ a = >, # = 1, electron in rela&ed state, n

we can calculate frequenc$ of this oscillation

e&pectation value that a particle can #e in a transition is
<x > = x m ( x, t ) 5 n ( x , t ) dx

if this e&pectation value = > #ecause the integral is Eero, there is no transition possi#le %ultiplied with the charge q, we have a dipole %o%ent

72

that radiates qS&C = (2 q a # cos (0%n t) x 5 dx ) 4 constant

q <x > =q

x ( x, t ) 5 ( x, t )dx
m n

which we can interpret as the e&pectation value is oscillating due to cos function, the frequenc$ of this oscillation is the difference of the eigenvalues of the functions divided #$ h#ar E E 0%n = = 2M f in other words, M7 = h '
m n

a)sence o' a t"ansition )ecause the inte#"a% is Ae"o is usua%%y desc"i)ed as a se%ection "u%e
for har%onic oscillatorK Pn = O 1, so there is no transition #etween n = 2 and n = 2, it is a%(ays one h' that is emitted o" a)so")ed, 3ust as 'lank had to assu%e in order to %ake his radiation for%ula fit the e&peri%ental data for infinite square well Pn = 1, ., 7 #ut not 2, 2 ,8
since, e/g/
(

>

sin(

2x x )dx sin( )dx = > ( (

77