Chapter 5 Quantum Mechanics

 limitation of Bohr theory:

1. Can not explain why certain spectral lines are more intense

than others.

2. many spectral lines actually consist of several separate lines

whose λ differ slightly.

3. an understanding of how individual atoms interact with one

another to from macroscopic matters Quantum

mechanics(1925~1926)

5.1 Quantum Mechanics

Classical mechanics future history of a particle is

completely determined by its initial position & momentum

together with force.

Quantum Mechanics suggest the nature of an observable

quantity uncertainty principle probabilities

classical mechanics is an approximate version of quantum

mechanics

Wave function φ.

 2
probability of finding the body for complex φ  2=

1
 * *
φ*φ (φ : complex conjugate)
* * 2 2
φ=A+ιB φ =A-ιB φ φ=A +B
“
 well behaved” wave function

(1)φmust be continuous & single-valued everywhere

(2)  x ,  y ,  z must be single valued & continuous(for

momentum consideration)

(3) φmust be normalization, which means thatφ must go to 0 as x

 y  z 

   dv needs to be a finite constant

2

 
2
= probability density P
 

 pdv  1   dv  1
2

 
normalization

px1 x 2    dx
2
probability
x1

 a particle in a box, φ=0 outside the box but in real case,

never happen.

2
5.2 wave equation
2 y 1 2 y
 solution: y=F(t  x/v)
 2 x v 2  2t

consider a wave equivalent of free particles.

ω
Y=Ae-i (t- x/v)
{undamped(constant amplitude A),

monochromatic( const ω), harmonic}

Y=Acosω(t – x/v)-iAsinω(t – x/v)

For a strenched string, only real part has significance.

3
5.3 Schrodinger’s equation : time dependent form
(t  x / v ) 2i (t  x
 for a free particle   Ae i  Ae 
)

h 2
 E  h  2 ,   
p p
 i ( Et  px)
   Ae h
............( A)

unrestricted particle of energy E & momentum P moving in

+x direction

(1)differentiating eq(A) for φ twice with respect to x

 2  p
 2 
x 2 
 2
p 2   2 2
x

(2) differentiating eq(A) forφwith respect to t

  iE
 
t 
  
E 
i t

for v<<c
p2
E  U ( x, t )
2m
p 2
 E   U
2m
   2  2
 i   U 
t 2m x 2
restrictio n  U

Derived from free particle, but it is a general case. If U known

φcan be solved.

4
5.4 Expectation value

calculated the expectation value <x>

 The value of x we would obtain if we measure the

positions of a great many particles described by the same

wave function at time t and then average the results.

 The average position x of a number of identical particles

distributed along x axis.

N1 at x1 , N2 at x2 ;……………

x
N1 x1  N 2 x2  N3 x3  .......

N xi i

N1  N 2  N3  ...... N i

 If along with a single particle,

 replaced Ni by probability Pi

pi   i dx
2

 x
2
dx
 x  



2
dx


If φ is a normalized function

  dx  1
2




x   x
2
dx

 Expectation value of position 
G x    G  x   dx
2



5
5.5 Schrodinger’s equation: steady-state form

for one-dimensional wave function Ψ of an unrestricted

particle may be written

   Et  px
 i   t
 iE   ip  x   t
 iE
  Ae  Ae e  
 e

  t
 iE
Ψ is the product of a time-dependent function e and a

position-dependent functionψ

If Ψ=F(x)×F'(t)

The time variations of all wave functions of particles acted on

by stationary forces have the same form as that of an

unrestricted particle.
  t
 iE
∵ substituting   e into time-dependent eq
  2  2
 i   U
t 2m x 2
 iE t   2  iE  t  2  iE t
 Ee   e  Ue 
2m x 2

  2m
2
 2  2 E  U   0
x 

Steady-state Schrodinger eq in 1-D

 2  2  2 2m
   E  U   0
x 2 y 2 z 2  2 3-D

6
** For Schrodinger’s steady-state eq, if it has one or more

solutions for a given system, each of these wave functions

corresponds to a specific value of energy E.  energy

quantization

 Considering standing waves in a stretched string of length L

that is fixed at both ends.

 these waves are subject to the condition(boundary condition)

that y=0 at both ends.


∵φ & need to be continuous, finite, and single-value
x

 λn=2L/n+1 , n=0,1,2,3……

 combination of wave eq & boundary condition.

 y(x,t) can exist only for certainλn

Eigenvalues & Eigenfunctions

The value of energy En for which Schrodinger’s steady-state eq

can be solved are called eigenvalues and the corresponding

wave functions φn are called eigenfunctions.

 The discrete energy levels of H atom

 me4  1 
En   , n  1,2,3,..........
32 2 o  2  n 2 
2

7
are an example of a set of eigenvalues.

In addition to E, angular momentum L is also quantized. In H

atom, the eigenvalues of the magnitude of the total angular

momentum are L  l i  1 , l  0,1,2,3............(n  1)

 A dynamic variable G may not be quantiaed.

 measurements of G made on a number of identical systems

will not yield a unique result but a spread of values which

average is expectation value.


G   G  dx
2



for example, in H atom, position x is not quantized.

8
5.6 particle in a box

 the motion of a particle is confined

between x=0 & x=L by infinitely hard

wall(it U(0)=U(L)=∞)

 A particle does not lose energy when

it collides with hard walls.

 U(0<x<L)=0=constant

 φis 0 for x  0 & x  L

within the box: d 2  2m2 E  0( U  0)........(5.24)

2

dx 

eq(5.24) has the solution

2mE 2mE
  A sin x  B cos x
 

B.C. φ=0 at x=0 & x=L

∵cos0=1 B=0 (∵φ(x=0)=0)

2mE
 ( x  L)  0  L  n n=1,2,3,……….


 energy of particle can have only certain values

eigenvalues energy levels

En= n 
2 2 2

n=1,2,3……….
2mL2
2mEn
 n  A sin x

n 2 2 nx
 En    n  A sin (eigenfunct ions )
2mL L

9
 these eigenfunction meet all requirements
 n
φn is a finite, single-valued, and n & continuous
x

(except at the ends of the box)

 To normalize φ

  dx  1
2
n


 nx 
L L
   n dx  A2  sin 2 
2
dx
0 0  L 
A2   2nx  
L L
  dx   cos dx 
2 0  L  
0
( sin 2  
1
1  cos 2  )
L 2
A2   L  2nx  L
  x   m  sin   A2    1
2    L 0 2
2
 A
L
2 nx
 n  sin , n  1,2,3.........
L L

10
 2 nx
* n  sin
L L

φn may be “-“ , but n

2
is “+”

(∵ n
2
is probability density of

finding the particle)

*when n=1 , the particle most likely to

be in the middle of the box but when

n
2
n=2 , =0 in the middle of the box.

Ex 5.3

Find the probability that a particle

trapped in a box L wide can be found

between 0.45L & 0.55L

For n=1 & n=2

11
Classically, we expect the particle to be in this region 10% of

the time ( 0.55  0.45L  0.1 ) but QM gives different prediction

L

depending on n
x2

Px1 , x 2  
2
n dx
x1

2nx
x
2 2
  sin 2 dx
L x1 L
2nx  2
x
x 1
  sin
 L 2n L  x1

∴ for n=1 , Px1 x2=19.8%

n=2 , Px1 x2=0.65%

12
ex 5.4

Find <x> of the position of a particle trapped in a box L wide

L
  2nx  


2

2 x

2

x sin  
 L   cos 
2nx
L


 
x dx

L : 4 4 n  8 n
2

<x>=   L L 
  0
2
2L L
 x    
L 4 2

Middle of the box !!

13
 5.7 finite potential well

*Potential energies are never ∞

consider potential wells with barriers of

finite height

*Particle energy E<U

classical mechanics: when particle strikes

the side of the well, it bounces off

without entering regions In QM, it has a

certain probability of penetrating into

regions Ⅰ&Ⅲ

*In Ⅰ&Ⅲ
 2 2m
 E  U   0
x 2  2
d 2
2
 a 2  0 x<0 , x>L
dx

2mU  E 
a

    Ae ax  Be  ax

ax -ax -ax
φⅢ = Ce +De ∵e ∞ when x -∞
ax
e ∞ when x ∞
ax -ax
∴ B=C=0  φⅠ=Ae , x<0 φⅢDe ,x>L

14
** these wave functions decrease exponentially inside the

barrier.

Within the well

2mE 2mE
 E sin x  F cos x
 φⅡ  

∵φ is continuous

∴φⅠ(x=0)=φⅡ(x=0) φⅡ(x=L)=φⅢ(x=L)
-aL
∴ A=F = De

 solve E (E≠0)

at x=0 & x=L is continuous
x

combining these B.C.  solve complete wave function

**Because the wavelengths that fit into the well are longer than for

an infinite well of the same width  particle momentum are lower

(∵P=h/λ)  En are lower than they are for a particle in an

infinite well  The wave function penetrates the walls, which

lowers the energy levels.

15
5.8 Tunnel effect

Particle strikes a potential U(E<U) the barrier has finite width (see

Fig 5.8)  particle has non-zero probability to pass through the

barrier & emerge on the other side.

Ex: tunnel diode: e' pass through potential barrier even though their

KE<barrier height

 In region Ⅰ&Ⅲ U=0

d 2  2m
 2 E   0
dx 2 

d 2 2m
 E  0
dx 2  2

   Ae ik x  Be ik x
1 1

  Fe ik x  Geik x
1 1
2mE p 2
k1=   (eq 5.43)
 ei  cos  i sin    
e  i  cos   i sin 

∴eq 5.43 the same as particle in a box

1  Aeik x 1
represents incoming wave

1  Be ik x 1
represent reflected wave

16
  φⅠ=φⅠ+ +φⅠ-

φⅢ+ = Fe ik1 x represented transmitted wave in region Ⅲ nothing

could reflect the wave

G  0  φⅢ=φⅢ+= Feik x 1

17
  v1= is the group velocity of incoming wave (equal to v of

particles)

 S  1 v 
2

is the flux of particles that arrives at the barrier,

# m
S= # of particles/m2sec ( )
m3 sec

 Transmission probability
2
  v FF * v 
T 
2
  v AA * v

classically T=0 ∵E<U

In region Ⅱ Sch eq
d 2  2m
 2 E  U    0
dx 2 
2 m E  U 
   Ce  k x  Dek x , k2 
2 2

(same as finite potential well)

∵exp are real quantities  φⅡ does not oscillate and   2 is not zero

 particle may emerge into Ⅲ or return toⅠ

18
 
applying B.C. & need to be continuous
x
  
d   d 
at x=o  (see Fig 5.9)
dx dx

at x=L φⅡ=φⅢ

dφⅡ/dx =dφⅢ/dx

 A+B=C+D

ik1 A  ik1B  k2C  k2 D

Ce  k 2 L  Dek 2 L  Fe ik1 L
 k2Ce  k 2 L  k2 Dek 2 L

 A  1 i  k k  1 i  k k 
       2  1  e(ik1  k 2 ) L     2  1 eik1  k 2 L
 F   2 4  k1 k2   2 4  k1 k2 

Let’s assume U>>E

2mE k2 k
k1    1
 k1 k2

2m( E  U ) k k k
k2   2 1  2
 k1 k2 k1

also assume L is wide enough  k2L>>1

e k 2 L  e  k 2
 A   1 ik 
      2 eik1  k 2 L
 F   2 4k1 
 A   1  ik 2   ik1  k 2 L
  *    e
 F   2 4k1 

+ - + -
Here vⅢ =vⅠ ∴vⅢ /vⅠ = 1

19
  
FF * v 
 AA *  1
16 
T  
      e  2 h2 L
 FF * 
2
AA * v  4   k2  
  k 
 1 
2mU  E  /  2 U
2
 k2 
     1
 k1  2mE /  2 E
approximation   1
 T  e 2k 2 L

20
5.9 Harmonic oscillator

Harmonic motion: the presence of a restoring force that acts to

return the system to its equilibrium configuration when it is

disturbed.

In the special case, the restoring force F follow Hook’s law 

2
d 2x h
F=-kx  -kx= m d x
  x0
dt 2 dt 2 m

 x  A cos2t   
1 k
 frequency of harmonic oscillator
2 m

A: amplitude

Φ: phase angle depends on what x is at t=0

In most of cases, restoring forces do not follow Hook’s low, but

when only consider a small displacement of x restoring

force can be exercised by Hook’s low.

 Any system in which something executes small vibrations about

an eqm position behaves like a simple harmonic oscillator.

21
.Maclaurin’s series
2 3
F(x)=Fx>0 + ( dF )x=0 X + 1/2( d F
)x=0 X2 + 1/6( d F
)x=0 X3 + ……
dx dx 2 dx 3

∵ x=0 is eqm position  Fx=0=0

2 3
for small x x ,x is much smaller than x  F(x)=(dF/dx)x=0 X

for restoring force (dF/dx)x=0 is negative  Hook’s law

2
.potential energy U(x)=-∫ 0x F(x)dx= k∫ 0x xdx=1/2kx

.sch eq
 2 2 2
+ 2m/h (E-1/2kx )φ=0……(5.75)
y 2
1/2 1/2
let c=(1/h hm ) , y=(1/h hm ) x=cx

 2    y     
=     c 
y 2 x  y x  x  y 

    y  2  
2
= c   
  c y 2
 y  y x 
2  2 2 2
 eq5.75  c +2m/  (E-1/2kx )φ=0
y 2
 2 2
 +2E/  ( m/k φ)- mk /  × x φ=0
y 2

 let α=2E/h( m/k )

 2
∴Sch eq (5.75) 
y 2
 
   y 2   0......5.74

for this eq, when y ∞ φ 0

for ∫  
2
dy=1

22
*for(5.78) only when α=2n+1 n=1,n=2,n=3……

can satisfy all conditions

∵α=2E/h( m/k )=2E/hν & α=2n+1

∴En=(n+1/2)hν n=0,n=1,n=2……

energy levels of Harmonic oscillator

Zero point energy E0=1/2(hν) ∴when T 0 E E0 not 0

23
 H atom

A particle in a box

A harmonic oscillator

“equally spaced & Eo

≠0”

24
for harmonic oscillator

each αn En φn
1
 2m  4 n 21
 
y 2

n    2 n! H n  y e 2

  

φn consists of a polynomial Hn(y)

(Hermit polynomial) see table 5.1

From Fig 5.12, the particle is able to

penetrate into classically forbidden

regions with an exponentially

decreasing probability.

25
 Classical: max at end

QM: Max at middle

n=0

QM: n=10

When n

QM classical

When n

penetration

Operators, eigenfunctions & eigenvalues


p   p
2
Is dx ??



E  E
2
dx ??


∵φ=φ(x,t), In order to carry out the integrations

 we need to express P&E as functions of x,t

but px   & Ex  

2 2

∴no function as p(x,t)&E(x,t)

 Integration form is not suitable for <P> <E>

26
    Et  px
 i
for free particle   Ae

 i  
 p  p  
x  i x
  i 
 E  E  i 
t  t
 
 P 
 i  x operator

E  i 
t
E  KE  U
1     2 2
2
p2
KE   KE    
2m 2m  i x  2m x 2

  2 2
i  U
t 2m x 2
   2  2
 i   U  sch eq
t 2m x 2
 
  
p     pdx      dx
   i x 

 
  dx
i  x

 
 
E     Edx 

    i t dx



= i     dx
 t

expectation value

of an operator Gx, p      Gdx


eigenvalue eq G n  Gn n

 2 2
H  U
Hamiltonian operator 2m x 2
 H n  En n

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 *Particle in a box
2 nx d 2 n nx
  n  sin  cos
L L dx L L L

   d 
   dx
p     pdx    i dx 
 

 2 n nx nx
L

i L L 0 sin
L
cos
L
dx

0
2 n
E  p  pn   2mEn    momentum
2m L

eigenvalue

± means that the particle is moving back & forth

average pav 
n L   n L  0
L

﹡Find momentum eigenfunction

 d 2 nx
p n  pn n p n  sin
i dx L L

φn is not momentum eigenfunction

 d  2 nx   n 2 nx
  sin  cos  pn n

i dx  L 
L  i L L L
e i  e  i 1 1
sin    ei  e  i
2i 2i 2i

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 1 2 inx L
 n  e
2i L
momentum eigenfunction
1 2  inx L
 n  e
2i L

Varity  n &  n are eigenfunction

p n  pn n
 d   1 2 in inx L n 
n  e   n  pn  n 
i dx c 2i L L L
 n
pn 
L
1 2 inx L
and n can be e
2i L
  n
similar pn 
L

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