REVIEW OF QUANTUM THEORY

Content
Chapter 1 Schrdinger Equation -- Approach to quantum mechanics
1-1 Origin of Schrodinger Equation
1-2 Time independent and dependent Schrdinger Equation
1-3 Physical Interpretation and Implication of Schrdinger Equation
Chapter 2 Applications of Schrdinger Equation to Time Independent Potential
2-1 Free Particle in 1D space
2-2 A particle in a 1D infinite potential well
2-3 Particle in 3-D Box (with infinite potential walls)
2-4 Position wave function and momentum wave function -Fourier
transform
2-5 Step Potential Wall
2-6 Single Potential Barrier: tunneling effect
Chapter 3 The Hydrogen atom
3-1 Schrodinger equation and solution of Hydrogen atom
3-2 Angular momentum
3-3 Zeeman effect
3-4 Spin of electron
3-5 Spin-orbit coupling
Chapter 4 Total Angular Momentum
Chapter 5 Harmonic Oscillator

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Chapter 1

Schrdinger Equation
-Approach to quantum mechanics

1-1 Origin of Schrodinger Equation

key observable properties of a particle
mass
position
momentum

m
x, y, z
px
py
pz
E

energy

Based on the classical wave equation and De Broglies matter wave concept,
Schrdinger postulated
[wave equation] must be valid and applicable in describing the matter wave like
particle, regardless of the specific energy or momentum
We except the solution to the wave equation must have the familiar form
(a)

( x, t ) Ae j ( kx t )

--------------- (1)

(assume 1D case)

(b) The wave equation contains appropriate derivatives of with respect to

d d 2 d
, 2 ,
dx dx dt
(c) Wave equation must be valid independent of the specific energy or momentum

coordinate and time

total energy of particle

P2
V (2)
2m

kinetic
energy

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Potentialenergy

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(1) Lets take the first derivatives of with respect to time

d
jAe j ( kx t )
dt

( E

Energy

(2) Second derivatives with respect to coordinates

2
Ak 2 e j ( kx t )
2
x

(k ) 2 P 2

Therefore, we can set the wave equation as

2
a( 2 ) bV
t
x

P2
E
V
2m

(3)

a, b constants to be determined
substitute (1), (2) into (3)

We obtain

a j

2m

The wave equation becomes

2 2

V 1D
t
2m x 2

2 2

V
j
3D
t
2m

TimedependentSchrdinger Eq.
j

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 Solution of Schrdinger equation

( x, t ) ( x) X (t)
We obtain
(1) ( x, t ) ( x ) X (t)

( ( x ) X (t )) E ( x ) X (t )
t
X (t )
E
j X (t )

X (t ) e

E
j t

j 2

h
h

e jt

(2)

2 2
[
V ] =E
2m
or

8 2 m
( 2 )( E V ) 0
h
2

Time independent Schrdinger equation

In classical mechanics, a particles total energy E can be expressed as

1
1 2
( Px2 Py2 Pz2 ) V (r ,t )
P (r , t ) V (r , t )
2m
2m

Also the Hamiltonian of a system total energy

i.e. H E

1 2 2 2
[Px +Py +Pz ]+V(r,t)
2m

Thus ,
(1) Schrdinger equation can be written in Hamiltonian form (operator form) as

(r , t )
H (r , t )
t

2 2
V ) --- Hamiltonian operator
where, H (
2m
(2) Comparison of classical mechanics expression with the wave equation:
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2 2
(
V )
t
2m
p2
V
E
2m
j

Quantum Mechanics

2 2
V

P2
V

x, y, z
m

x, y, z
m

Classical

observable!

Thus , Schrdinger proposed & defined

Energy operator:

Momentum operator px2

2 2x

Allobservablesare
expressedinoperation
form

py2 22y
pz2 2 2z

px

j x

py

j y

pz

j z

Schrdinger equation in operator form becomes

E=H
eigenfunction
E:eigenvalueoftheoperatorH
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1-2 Time independent and dependent Schrdinger Equation

Assume a solution of Schrdinger equation is

( x, t ) ( x ) X (t )
Then , substitute it into Schrdinger equation
We have
(1)

( x, t )
E ( x, t ) 1
t

X (t ) e

E
j t

=e jt

(2)

or

2 2
V ( x) E
2m x 2

2 2
V (r )] E
2m

---

Time independent Schrdinger equation

2m
[ E V ] 0
2
8 2 m
2
( 2 )( E V ) 0
h
2

2 ( E V ) 0
2m
2

If V is known, then all allowed

and E can be calculated.

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 Multiple solutions for & E

1 E1

E2

2 E2

E1

3 E3

Only very particular V(r) can be solved analytically

e. g.

Square Quantum well

Atom

Periodical atom
V ( x) V ( x a)

Parabolic well (Harmonic

oscillator)

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1-3 Physical Interpretation and Implication of Schrdinger Equation

(1) Schrdinger
*
*

-----

dont exactly know

but can explain atomic spectrum well
cant explain photoelectric effect
cant fit plank formula

(2) Max Born(1926)

--

probability amplitude of electron @

particular position in time

--

--

of associate particle
Atomic picture becomes

physical probability density of the presence

Bohr

Characteristics of Schrdinger equation:

(1)

Probability density
suppose is a complex function of a particle
2

* = = real quantity

x
x0
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If
then

has a functional dependence (as previous pic.)

2

* dx dx
b

then

* dx const.
a

In 3-D case (particle in confined volume-V)

* dr

--- Normalization

1 Dirac representation (bracket expression or Dirac notation)

( x)

Kat one state in QM system

* ( x)

Bra conjugate of

(2) orthogonality
In Cartesian coordinates

e1 , e2 , e3

3-coordinates

are orthogonal

1, i j
ei e j ij
0 , i j
These unit vectors form a complete orthogonal set

Similar
H i Ei i

There are many

1 , 2, eigen function

corresponding to E1 , E2, eigen value

If

s are normalized and form a complete orthogonal set then

*
i

1, i j
dr 3 ij
0, i j

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(3) Expectation value

Define a position r for state (observable)

< r > = expectation values

r P(r,t)d 3 r * ( r , t )r (r , t )d 3 r

rd 3 r r
2

similar

E * j d 3r E
t
P *( j ) d 3 r

From H i Ei i

*
i

* i*

H i dV i* Ei i dV Ei i* i dV

E j * H j dV H

H E
Example

2
L

( ) 2 sin

If

x
L

0 x L 1D infinite potential

x * x dx
2
x
L
( ) x sin 2 ( )dx
L 0
L
2
L

2
x
x
P j ( ) sin( ) cos( )dx 0
L
L L
L

L
2

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(4) Heisenberg's Uncertainty Principle (HUP)

Definition the root-mean-squared deviation from the mean <x>

x 2 ( x x ) 2
x 2 2 x x x 2

x 2 2 x x x 2
x 2 2 x 2 x 2
x 2 x 2

similar
px 2 px2 px 2

where
x *j x j dx
x 2 *j x 2 j dx
px j j
px2 2 j

j
x
2 j
x 2

dx
dx

From previous example

2
L

( x) ( ) 2 sin(

x
L

1
1
1
x 2 x 2 x 2 L2 ( 2 )
3 2
4
x 0.17 L

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Similar

So

x p 0.17 L

1
0.55 meet HUP!
2
L

(5) Probability density flow

For quantum system

2 2
j

V
2m
t
*
2 2 *
j

V *
2m
t

--- (1)
--- (2)

conjugate
We use (1) * (2) to eliminate V

*
2 2 *
[ 2 * ]

2m
t
2 2
j
[ * * ]
2m
t
2

[ * * ]
2m
2

[ * * ]
2m
j

The above equation is similar to the continuity equation of charge density

J
t

J 0
t

[ * * ] J
t
2mj

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[ * * ]= Probability density current !!

2mj

We can also obtain probability density current from

d r 1 dr
*

*
*
*
*
( )

t t
t
t
From eqs. (1) and (2) and multiply the above eq. as * and with

&
t

*
t

( * * )]
[
2mj
t
J

(6) Non-Commuting Operators

The momentum operator in the position representation is a differential operator

p j
Thus

operator on x

[ x, p] xp px

operator on

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 [ x, p ]

Find

( xp px) dx
xp px dx
*

* ( x )]dx
x
x

j [ * x * ( x
)]dx
x
x

j [ * x
* x
* )]dx
x
x

j [ * x

j * dx
j
[ x, p] xp px j

or using bra-ket

[ x, p ] j x
x
x
x

j x x
x
x

or

[ x, p] ( xp px)

x( j ) j ( x )
x
x

j x j [ x ]
x
x
j

[ x, p ] j

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Chapter 2 Applications of Schrdinger Equation to Time

Independent Potential
2-1 Free Particle in 1D space
If V = 0 throughout all space, then Schrdinger equation becomes

d 2 2m
E 0

dx 2 2
Solution ( x) Ae jkx Be jkx
where
or

---

(1)

2mE
2mE

2 2
k
E=
--- (2)
2m
k

(1) All values of E0 are allowed

(2) No quantization of E values
(Continuous, not discrete energy)
(3) All value of E<0 are not allowed
(Because wave function becomes real and positive exponential with one
approaches )

( x) Ae

2 mE

Be

2 mE
2

(4)Both terms of above solution in eq. (1) represent independent solution,

with the same energy for k. Thus, the solutions are doubly degenerate!!
(5)Since E from eq. (2)
2k 2
2m
k 2

2m

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Dispersionrelationship

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Parabolic curves

(6) De Broglie wave

h
p

p k

2mE
2mE

2mE

2-2 A particle in a 1D infinite potential well

V 0

V=,
V=0,

x<0
:
0xL :

region II
region I

V=,

x>L

region III

Now, we list Schrdinger equations for all regions (I, II, III)
In region I,
d 2 2 2m
2 [ E V ( x)] 0
dx 2

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--- (1)

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Since in region II and III, V

II , III 0

to satisfy (1).

Inside the well V 0

d 2 2m
E0

--- same as free particle

dx 2 2
I Ae jkx Be jkx
2mE

Boundary conditions are

(a) =0 x=0,L

dx 1
*

(b)

From the above condition (1)

0 A B

jkL
jkL
0 Ae Be

(2)
(3)

We need to solve for coefficients A and B.

For non-zero solutions, we must have:

jkL

jkL

e jkL e jkL 0

sin(kL) 0
kL n , n is integer

n
L

So,
2 k 2 n 2 2 2
En

2m
2mL2

--- energy is quantized

The wave function becomes

n Ae

n
x
L

Be

n
x
L

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From (2) , A+B=0 , A=B

n A[e

n x
L

=Cn [sin

n x
L

n x
]
L

n*n dx 1
L

n*n dx Cn2 sin 2 (

L

sin

n
x)dx 1
L

n x
L n x 1
2 nx L L
sin
dx
[
]0
L
n 2 L 4
L
2

2 1
Cn ( ) 2
L
Thus

2
L

n ( ) 2 sin(

n x
)
L

Standing wave

2 1

1 ( ) 2 sin( x)
L
L
2 1
2
2 ( ) 2 sin( x)
L
L
2 1
3
3 ( ) 2 sin( x)
L
L

Review of Quantum Mechanics

2 2
E1
2mL2
4 2 2
E2
2mL2
9 2 2
E3
2mL2

Groundstate

1stexcitedstate

2ndexcitedstate

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En
2
(
)
2mL2
2

8
7
6

4
3

En

E6

E5

E4
E3
E2
E1
n

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 Physical interpretations gained from this example

(1) For a confined particle, the solutions of Schrdinger equation

H n Enn
have a set of eigen functions n
where

and eigenvalues En

2 1
n x
)
L
L
n 2 2 2
En
2mL2

n ( ) 2 sin(

(2) orthogonality of n exist for

L

dx
*
n n

mn

(3) Probability of finding the particle anywhere within the well

n=1 : ground state
L

x 1 x 1 1* x1dx
0

L
2

n=21st excited state

L
L 3L
,
2 , but the highest probability density occurs at 4 4

n=32nd excited state

L
L L 5L
, ,
2 , but the highest probability density occurs at 6 2 6

(4) The allowed energies become discrete and separation becomes large as n
increases
(5) As n increases to large number, n

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becomes near uniform distribution

Tien-chang Lu

2-3 Particle in 3-D Box (with infinite potential walls)

z

V 0 inside the box

L

V outside the box

V 0
L

Schrodinger equation inside the box

2 2
( x, y, z )
E 0
2m
Separation of variables
set ( x, y, z ) ( x) ( y ) ( z )
Then
2 1 2 ( x )
1 2 ( y )
1 2 ( z )
[

] E
2m ( x ) x 2
( y ) y 2
( z ) z 2
Then
2 1 2 ( x)
2m ( x) x 2 E1

2 1 2 ( y )
E2

2
2m ( y ) y
2 1 2 ( z )
E3

2
2m ( z ) z

E1 E2 E3 E

Solutions are (based on previous 1D example)

( x) A1 cos k1 x A2 sin k1 x
( y ) B1 cos k2 y B2 sin k2 y
( z ) C1 cos k3 z C2 sin k3 z
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k1

2mE1
2

k2

2mE2
2

k3

2mE3
2
Tien-chang Lu

Boundary conditions require that 0 at (x,y,z)=0

thus
& 0 at (x,y,z)=L

A1=B1=C1=0

thus
2 2

E
n
(
)
x
1
2
2
mL

2 2

2
)
E2 n y (
2mL2

2 2

E
n
(
)
3
z
2mL2

nx 1, 2,3
n y 1, 2,3
nz 1, 2,3

2 2 2
[ nx n y2 nz2 ]
2mL2
The eigen function
Enx ,ny ,nz

nx ,ny ,nz Axyz sin(

using

dxdydz 1
Axyz (

ny
nx x
nz
) sin( y ) sin( z )
L
L
L

8 12
)
L3

n y
n x
n z
2 3
( ) 2 sin( x ) sin( y ) sin( z )
L
L
L
L

Ex

nx 2, n y 2, nz 3

E322 E232 E223

2 2 2 2 2
2 2

[2 2 3 ] 17
2mL2
2mL2

degenerate states !!

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However, the wavefunctions are different!

2

322

3
2
2
2 3
y ) sin(
z)
sin( x) sin(
L
L
L
L

232

2
3
2
2 3
sin(
x) sin( y ) sin(
z)
L
L
L
L

223

2
2
3
2 3
sin(
x) sin(
y ) sin( z )
L
L
L
L

Thus, the state is three-fold-degenerate!

2-4 Position wave function and momentum wave function - Fourier

transform
Sometimes it is desired to represent wave function in spatial frequency domain

1
( x)
2

( k )e

jkx

dk

where

(k ) Fourier transform of ( x )
k spatial frequency related to momentum by
p k
Thus, (k ) momentum wave function
Similarly (k ) can be transformed back to position wave function

1
(k )
2

( x )e

jkx

( x)

by

dx

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Example
1

( x)

(2 ) 4

x2
)
4 2

: Gaussian wave function

Find <x> and x

Sol:

(1)
x

1
1

(2 ) 2

x2
2 2

xdx 0

(2)

x 2 x x 2 x 2 x 2

x 2 2

Find p
Sol:

1
(k )
( x)e jkx dx

2
2 2
2 1
( ) 4 e k

(k ) k (k )dk

2 1
( ) 2

ke

2 2 k 2

dk

2 2

e 2 x
( ) [
]

4 2
0

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2
2

(k )k (k )dk

2 12
2 2 2 k 2

k
(
)

e dk

12
(
)

2 12
2
( )

4 3
1

4 2

p k
p 2 2 k 2
2 [ k 2 k 2 ]
2[

1
4 2

0]

4 2

HUP

x p

2 2

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2-5 Step Potential Wall

Apply to:
Schottky barriers
Thermionic emission
Field emission

jkx
Ae

jkx
Be

V0
Ce rx

V ( x ) V0 ( x )

( x ) 1, x 0

( x ) : Heavyside step function

( x ) 0, x 0
V 0
0

Assume E V0 : incident energy<potential energy

(1)

For x<0 , V ( x) 0

Assume

( x) Ae jkx Be jkx : plane wave

Ae jkx incident wave

Be jkx reflected wave

(2)

2mE

2
For x>0 , V ( x) V0 : non-propagating wave
k

Assume
( x) Ce rx

2m V0 E
2

for E V0

Boundary conditions
, ' continuous at x 0

Thus, we have

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A B C

jk A B rC

We can express two coefficients B & C in term of A

r
: A B C

jk

C

A

B
-
A

From

incident & reflected probability are equal

B

1 : phase different

A
no transmitted probability

@ x 0

2 jk
jk r

jk r
jk r

k 2 r 2 1
B

A
k 2 r 2 2

r
where 2 tan 1
k

( x ) A e jkx e j kx

( x ) 2 A 1 cos 2kx
2

standing wave

2 k
2A

2k

2k

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:x

2k

:x
2k

( x ) 4 A2
2

( x) 0
( x ) 2 A 1 cos
2

:x 0

2 tan 1

V0
1
E

: x 0 when V0 ,

2 (0) 0
Infinite barrier case!

ExamplePenetration depth

Assume the incident electron is traveling at a velocity

105 m / sec into the barrier V0 2 E at x 0

E

V0 2 E

1 2
m 4.56 1021 J 2.85 102 eV
2

II ( x ) A2e rx

II

Define Penetration depth as e

then rd 1

2m V0 E
2

point at x d

2
2
1.054 1034
d

2m V0 E
2m 2 E E
2 9.111031 4.56 1021

1/ 2

11.6

d ~2 lattice constant

If V0 10 E

2
2.9
2m 10 E E

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2-6 Single Potential Barrier: tunneling effect

V ( x) V0 , 0 x a

x 0

(
)
0,
V
x

x a

V ( x)

A1e

V0

jk1 x

A3e jk1x

B1e jk1x

x
0

II

III

a: Potential barrier width assume it is small!

Case(1): E V0

jk x
jk x
Region I :V 0, 1 A1e 1 B1e 1 ,

Region II :V V0 , 2 A2 e jk2 x B2 e jk2 x ,

Region III:V 0, 3 A3e jk1x ,

only out-going wave

k1
k2
k1

2mE
2
2m E V0
2

2mE
2

Boundary conditions:

A1 B1 A2 B2

x0
k1 A1 B1 k2 A2 B2

jk2 a
jk2 a
jk1a

A
e
B
e
A
e
2
2
3

x a k A e jk2a B e jk2a k A e jk1a

2
1 3
2 2

A1 , B1 , A2 , B2 , A3 5 unknowns, 4 equations

By eliminating A2 , B2 ,

k12 k2 2 1 e 2 jk2 a
B1

A1 k1 k2 2 k1 k2 2 e2 jk2 a

: Reflectance

A3
4k1k2 e j k2 k1 a

A1 k1 k2 2 k1 k2 2 e 2 jk2 a

: Transmittance

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Definition:
Probability of transmission Transmission coefficient

Transmission coefficient

2
2

k12 k2 2 sin 2 k2 a
A3

T
1

A1
4k12 k2 2

:Tunneling probability

V0 2 sin 2 k2 a
1

4 E E V0
4 E E - V0
2 2
V0 sin k2 a 4 E E V0

Similar to FP interference!!

Reflection coefficient
1

4E E V
B
R 1 1 2 2 0
A1
V0 sin k2 a
V 2 sin 2 k2 a
2 20
:Reflection probability
V0 sin k2 a 4 E E V0
2

reflection exist even E V0

Of course R T 1

T
1

V0
sin 2 k2 a
4 E E V0
2m E V0

k2 a

2
2
2
E V0
ka
2 2
2ma
@ k2 a n , n 1, 2,3...

Tmax 1

Tmin

1
V0 2
1
4 E E V0

1 3 5
@ k2 a n ' , n ' , , ...
2 2 2

1
ma 2V0 2 1
1

2
2 E k2 a

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Resonant
scatting
1

/2

3 / 2

5 / 2

k2a

Example: V0 = 3 eV, a = 10 A;
1.0

0.8

0.6

0.4

0.2

10

15

20

x axis is normalized to

E V0
2 2
2ma 2

Example: V0 = 1 eV, a = 5 A;
1.0

0.8

0.6

0.4

0.2

10

15

20

x axis is normalized to

E V0
2 2
2ma 2

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As k2 a
E V0

2mE
k2
2
like a free electron!!

Case(2): E V0

From the above result,

1
T

2
V0
2
1
sin k2 a
4 E E V0
Since E V0 , k2 a

So, we obtain

2m E V0

V0
(k2 a ) 2
4 E E V0

T depends on

a very small

k2 2
2m
2 , and sin k2a k2a, and E V0
E V0

mV0 a 2
1
2 2

mV0 a 2

2 2

Case(3): E V0

k'

2m V0 E

jk2

Thus

V 2 sinh 2 k ' a
T 1 0

4 E V0 E

4 E V0 E

Hyperbolic sin:

V0 sinh 2 k ' a 4 E V0 E
2

sin jk2 j sinh k2

Note:

1 x x
sinh x 2 e e

4 E V E
R 1 2 0 2

V0 sinh k ' a
Review of Quantum Mechanics

p32

Tien-chang Lu

(1) When potential barrier is weak

k ' a 1
i.e.

sinh 2 k ' a k ' a

k '2

1
2

V0
2
1
k 'a
4 E V0 E

2m V0 E
2

T
1

2m V0 E
V0 a

4 E V0 E
2
2

ma 2V0
plot T vs E / V0 for
2
2

1
1

2
2 2
ma V0 V0
ma V0
1
1 2 2 E
2

2 E

T
1
0.8

0.6
0.4
0.2

0.2

0.4

0.6

0.8

EVo

(2) Strong potential barrier k ' a 1

1 x x
e e ,
2
1
ex
2
1
sinh 2 x e 2 x
4
sinh x

x 1

1 2k 'a
V0
1
e
4 E V0 E 4

Review of Quantum Mechanics

p33

Tien-chang Lu

16 E V0 E

2 k ' a

e
V0 2
clearly

exponential
1

decay!!

Note that, for the original transmission equation:

1
V0 2 sinh 2 k ' a

T 1

4 E V0 E

T
1

0.8

0.6

0.4

0.2

4 E V0 E

V0 sinh 2 k ' a 4 E V0 E
2

2m
a 5, 1, 0.1, then

If

0.1

0.2

0.4

0.6

0.8

EVo

Please refer to the following link:

http://phet.colorado.edu/en/simulations/translated/zh_TW

Review of Quantum Mechanics

p34

Tien-chang Lu