Winter 2013 Chem 356: Introductory Quantum Mechanics

34



Chapter 3 Schrodinger Equation, Particle in a Box .................................................................................. 34
Introduction to the Schrodinger Equation .............................................................................................. 34
Linear Operators ..................................................................................................................................... 36
Quantization of energy ........................................................................................................................... 39
Interpretation of Wave Function ............................................................................................................ 40
Determination of Constant C .................................................................................................................. 41
Useful integrals for particle in the box ................................................................................................... 43
Demonstration of Uncertainty Principle ................................................................................................. 44
Particle in a 3 dimensional box ............................................................................................................... 46



Chapter 3 Schrodinger Equation, Particle in a Box
Introduction to the Schrodinger Equation
De Broglie suggested one can associate a wave with a particle and take
h
p

=

ikx
e
2
k
t
=
2
h
p k k
t
= =
Generalization to 3 dimensional wave

ikx
e p k =

In chapter 2 we saw that waves in general satisfy a wave equation.
Try to postulate a wave equation for electron-waves (a guess)
Provide some rational for Schrodinger equation:
Wave equation
2 2
2 2 2
1 u u
x t
V
c c
= =
c c

Choose solution with particular
2
v
e
t
=
( , ) ( )cos( ) u x t x t e =
Winter 2013 Chem 356: Introductory Quantum Mechanics

Chapter 3 Schrodinger Equation, Particle in a Box 35


2 2
2 2
d
dx
V
e
+ ( ) 0 x =
2 v e t = V v = v (nu) frequency ; V velocity


2 2
2 2
4
( ) 0
d
x
dx
t

+ =

h
p
=
2
2 2
2
2 2
4 4 p
p
h
t t

| |
= =
|
\ .


2
2 2
2
( ) 0 p x
dx

c
+ =
Now substitute
2
p
:


2
2
p
V E
m
+ =

2 2 2
2
( ) 0
2 2
p
x
m m x

c
+ =
c


2 2
2
( ) ( ) 0
2
E V x
m x

c
+ =
c

Or
2 2
2
( ) ( ) ( )
2
E x V x x
m x

c
= +
c


( ) H x


We obtain a differential equation for function ( ) x

( ) ( ) H x E x =
E is a constant, the energy

H is operator that acts on a function.

Summarizing:
1)
2
2 2
2
( ) p x
x

c
=
c
(using de Broglie + classical wave equation)
2) Substitute
2
2 ( ( )) p m E V x =
2 2
2
( ) ( ) ( )
2
V x x E x
m x

c
+ =
c

( ) ( ) H x E x =
2

( )
2
p
H V x
m
= + energy operator (see later)
Winter 2013 Chem 356: Introductory Quantum Mechanics

Chapter 3 Schrodinger Equation, Particle in a Box 36


We need to discuss 2 mathematical items

a) Operators p ,

H ,
2
p .?
b) Eigenvalue equations

H E = , E p: numbers
p p =
Operators will be indicated by ^ hat or carot


Linear Operators
(in 1 dimension first)

( ) ( ) Af x g x =

Acting with an operator on a function yields a new function.

A
( ) f x

( ) ( ) Af x g x =
2
2
d
dx
2x 0
2
2
2 3
d d
dx dx
| |
+ +
|
\ .

3
x
2 3
6 6 3 x x x + +
d
x
dx

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

2
x
2 2
( ) 3
d
x x
dx
=
d
i
dx

ikx
e
ikx
ke
2
2
( )
2
d
V x
m dx
| |
+
|
\ .
cos( ) kx
2 2
( ) cos( )
2
k
V x kx
m
| |
+
|
\ .



The operators we consider are linear operators:

1 1 2 2

( ( ) ( )) A c f x c f x +
=
( ) ( ) 1 1 2 2

( ) ( ) c Af x c Af x +
Where
1
c ,
2
c are (complex) constants

Winter 2013 Chem 356: Introductory Quantum Mechanics

Chapter 3 Schrodinger Equation, Particle in a Box 37

Example of operator that is not linear: SQR( ( )) f x
2
( ( )) f x

2 2
SQR( ( ) ( )) ( ( )) ( ( )) 2 ( ) ( ) f x g x f x g x f x g x + = + +
=SQR( ( )) SQR( ( )) 2 ( ) ( ) f x g x f x g x + +

Not linear therefore
We can act with operators in sequence


( ) ( ( )) ABf x A Bf x =
In general:


( ) ( ) ABf x BAf x =
Example

A x = ,

d
B
dx
=
( )
d df
x f x x
dx dx
| |
=
|
\ .

( ) ( ( )) ( )
d d df
x f x xf x f x x
dx dx dx
| |
= = +
|
\ .


If

( ) ( ) ABf x BAf x = , for any ( ) f x we write


0 AB BA =


[ , ] 0 A B =

A and

B commute, the order does not matter

Eigenvalue equations (by example)

( ) ( ) A x a x =
Acting with

A on a function yields the same function multiplied by a constant

( )( )
ikx ikx
i e i ik e
x
c
=
c


ikx
ke =

2
2
ikx
h
e
t
t
| |
=
|
\ .


ikx ikx
h
e pe

= =

2
i x
ikx
e e
t

= periodic with period

We say
x
p i
x
c
=
c


ikx ikx
x x
p e p e =
Number

Winter 2013 Chem 356: Introductory Quantum Mechanics

Chapter 3 Schrodinger Equation, Particle in a Box 38

The wave function
ikx
e is an eigenfunction of operator
x
p

x
d
p i
dx
= , with eigenvalue

h
k

=
( ) ( ) p x p x =
A particle with definite momentum
x
p is described by eigenfunction of operator
x
p

Consider kinetic energy operator
2
2 2 2
2

2 2 2
i
p d x
m m m dx
c | |

|
c
\ .
= =
Eigenfunctions of Kinetic energy:

2 2 2 2
2
2 2
ax
d a
e
m m dx
= 0 !! < (if areal)
Not physical

2 2 2
2
2
sin( ) + sin( )
2 2
d
ax a ax
m m dx
=

Constant Eigenvalue
Or
2 2 2
2
2
cos( ) cos( )
2 2
d
ax a ax
m m dx
=
Also
iax
e
2
2
2
iax
a e
m

Or Hamiltonian operator:

2

( )
2
p
H V x
m
= +
2 2
2
= ( )
2
V x
m x
c
+
c

( ) ( ) H x E x =
: particle described by eigenfunction ( ) x has the definite energy E





Winter 2013 Chem 356: Introductory Quantum Mechanics

Chapter 3 Schrodinger Equation, Particle in a Box 39


Quantization of energy

We saw that a fundamental feature of new quantum mechanics was that energy cannot take
on any value, but only certain values. Why is that?

Let us consider a particle in a box problem:

( ) 0 V x = 0 x a < <

( ) V x = elsewhere


We wish to solve

2 2
2
( ) ( ) ( ) ( )
2
d
x V x x E x
m dx
+ =
Constant

Outside the box ( ) V x we want finite values of E , the only possibility is ( ) 0 x = outside the box.

We also wish ( ) x to be continuous:

Inside the box we have 0 V =

2 2
2
( )
2
d
E x
m dx

=

Boundary Condition: (0) ( ) 0 a = =

We considered before this equation

General Solution: sin( ) cos( ) c kx b kx +
0 x = 0 = 0 b =
2 2
2
k
E
m
=
Winter 2013 Chem 356: Introductory Quantum Mechanics

Chapter 3 Schrodinger Equation, Particle in a Box 40

x a = sin( ) 0 c ka = , 1, 2, 3
n
k n
a
t
= =
Any c , c not equal to 0
( ) sin
n x
x c
a
t

| |
=
|
\ .


2 2 2 2 2
2 8
n h n
E
ma ma
t
= = 1, 2, 3..... n =

- Quantization: Combination of wave equation + Boundary conditions
- 1, 2, 3 n = also possible, but yields same solutions
sin sin
n x n x
c c
a a
t t | |
=
|
\ .

- c can be anything (still)

( ) ( ) Ac x cA x =
( ) ca x =
( ( )) a c x =

If ( ) x is an eigenfunction of operator

A then also ( ) c x is eigenfunction. ( c is constant)

Interpretation of Wave Function

In Mathchapter B we discussed probability distribution ( ) p x dx :

( ) 0 p x > x
( ) 1 p x dx

=
}

( ) x xp x dx

=
}
etc.
The absolute square of the wave function
2
*
( ) ( ) ( ) x x x = is to be interpreted like a probability
distribution.

2
( ) ( ) p x dx x dx =
Probability to find particle between x and x dx +

( ) ( ) ( ) x f x ig x = + complex
( ) f x , ( ) g x real
Winter 2013 Chem 356: Introductory Quantum Mechanics

Chapter 3 Schrodinger Equation, Particle in a Box 41


*
( ) ( ) ( ) x f x ig x =


*
( ) ( ) [ ( ) ( )][ ( ) ( )] x x f x ig x f x ig x = +

2 2
( ) ( ) [ ( ) ( ) ( ) ( )] f x g x i f x g x g x f x = + +
So
2
( ) x 0 > everywhere
Probability distribution

Moreover:
2
( ) 1 x dx

}

Normalization
Multiply ( ) x by constant c , choose c such that ( ) ( )
new
c x x = is normalized

Particle in the box (later)

2
( ) sin
n
n x
x
a a
t

| |
=
|
\ .

Further Interpretation

*
( ) ( )
high
low
x
x
x x dx
}

Probability to find particle between
low
x and
high
x
And

*
( ) ( ) x x x x dx =
}


Determination of Constant C

We will impose that the wave functions are normalized

*
( ) ( ) 1 x x dx

}
For reasons discussed before
*
( ) x : complex conjugate of functions
( ) ( ) ( ) x f x ig x = + ( ) f x , ( ) g x real

*
( ) ( ) ( ) x f x ig x =

*
( ) ( ) [ ( ) ( )][ ( ) ( )] x x f x ig x f x ig x = +

2 2
[ ( )] [ ( )] [ ( ) ( ) ( ) ( )] f x g x i f x g x g x f x = + +

2 2
( ) ( ) f x g x = +
Winter 2013 Chem 356: Introductory Quantum Mechanics

Chapter 3 Schrodinger Equation, Particle in a Box 42


2
( ) x = 0 > everywhere
If ( ) x is real then
2
2
( ) ( ) x x =

Consider particle in the box wave functions:
( )
n
x = sin
n
n x
C
a
t
0 x a s s
0

2
2
2
0
( ) sin
a
n
n x
x dx C dx
a
t

| |
=
|
\ .
} }


2
1
2
n
a
C = =
Choose
2
i
n
C e
a
u
=
Simplest,
2
ik
e
a
would work too.
We can always choose the function ( ) x to be normalized
A physically meaningful wave function would be normalized
If

( ) ( ) A x a x = eigenfunction of

A, eigenvalue a
Then
( )
*

( ) ( ) x A x

*
( ) ( ) x a x =
*
( ) ( ) a x x =
And:
( )
*

( ) ( ) x A x dx

}


*
( ) ( ) a x x dx

=
}

1 a = IF ( ) x is normalized
We define:

*

( ) ( ) A x A x dx =
}

Called the expectation value of operation

A, depending on ( ) x , also called the
average value of

A


If ( ) x is normalized, then

A would be the average value measured for quantity A

If ( ) x is an eigenfunction of

A, then one would always measure a , and the average

value A a = IF ( ) x is normalized
Winter 2013 Chem 356: Introductory Quantum Mechanics

Chapter 3 Schrodinger Equation, Particle in a Box 43


If ( ) x is not an eigenfunction of

A, then many values could be obtained if A is measured.

The average value would be

A

One more definition:
( )
2

A A : The standard deviation from the average. The spread of the measured
values

( )( )

A A A A

2
2

2 A A A A = +

2
2

2 A A A A = +

2
2

A A =

2
A
o = Depends on wave function ( ) x

Useful integrals for particle in the box

2
sin 2
sin
2 4
x ax
axdx
a
=
}


2
2
2
sin 2 cos 2
sin
4 4 8
x x ax ax
x axdx
a a
=
}


3 2
2 2
3 2
1 cos 2
sin sin 2
6 4 8 4
x x ax
x axdx ax x
a a a
| |
=
|
\ .
}

Definite Integrals (Most important)

2
0
sin
2
a
n x a
dx
a
t
=
}


2
2
0
sin
4
a
n x a
x dx
a
t
=
}


3 3
2 2
2 2
0
sin
6 4
a
n x a a
x dx
a n
t
t
=
}


0
sin cos 0
a
n x n x
dx
a a
t t
=
}


Winter 2013 Chem 356: Introductory Quantum Mechanics

Chapter 3 Schrodinger Equation, Particle in a Box 44


Demonstration of Uncertainty Principle

Using the above integrals, we can calculate the following
a) Normalize sin
n n
n x
C
a
t
=
2
2 2
0
sin 1
2
a
n n
n x a
C dx C
a
t | |
=
|
\ .
}

2
n
C C
a
= =
Normalized particle in the box eigen states:
2
sin
n x
a a
t | |
|
\ .

b) Calculate x for normalized ( )
n
x :
0
2
sin sin
a
n x n x
x x dx
a a a
t t
=
}


2
2
4 2
a a
a
= = center of the box
c) Calculate
2
x
2 2
0
2
sin sin
a
n x n x
x x dx
a a a
t t
=
}


3 3 2 2
2 2 2 2
2
6 3 4 2
a a a a
a n n t t
| |
= =
|
\ .

d) Standard deviation in x :
2
2 2
x
x x o =

2 2
2 2 2 2 2 2
2 2 2 2
2
3 2 12 2 3 2 2
a a a a a a n
n n n
t
t t t
(
| | | |
= = =
| | (
\ . \ .


e)
0
2
sin sin
a
x
n x d n x
P i dx
a a dx a
t t | |
=
|
\ .
}

0
2
sin cos 0
a
n n x n x
i dx
a a a a
t t t | |
= =
|
\ .
}

f)
2
2 2
2
0
2
sin sin
a
x
n x d n x
P
a a a dx
t t | |
=
|
\ .
}


2
2 2
2
2
0
2
sin
a
n n x
dx
a a a
t t | |
=
|
\ .
}

2
a

Winter 2013 Chem 356: Introductory Quantum Mechanics

Chapter 3 Schrodinger Equation, Particle in a Box 45


2 2 2 2 2
2 2
4
n h n
a a
t
= = ( 2
n
mE = , of course!)
( )
2
x
hn
P
a
o =

We can test the Heisenberg Uncertainty Principle

1
2 2
2
2
2 3 2
x p
a n hn
n a
t
o o
t
(
=
(



1
2 2
2
2
2 3
n t (
=
(


2
>
Note 1:
12
x
a
o as n

is the same as uncertainty in uniform distribution:

2
0
1
2 2
a
x a
x
a
= =
2 3 2
0
1 1 1
3 3
a
x x a
a
= =
2 2 2
3 4 12
x
uniform
a a a
o = =

x
P
o grows with n. Why?

2 2 2
2
(2 )
n n
n
P mE
a
t
= =

Spiked distribution
Large Uncertainty
This represents the classical limit of particle of
energy
n
E bouncing back and forth in the box
Note 2: x ,
2
x ,
x
P ,
2
x
P Can
be calculated for any wave function
for example: ( ) ( ) x Cx a x = also satisfies the boundary conditions

Winter 2013 Chem 356: Introductory Quantum Mechanics

Chapter 3 Schrodinger Equation, Particle in a Box 46


Particle in a 3 dimensional box



Consider rectangular box of length , , a b c

3D Schrodinger Equation:

2 2 2 2
2 2 2
( , , )
2
x y z
m dx dy dz

| | c c c
+ +
|
\ .
( , , ) E x y z =
Boundary Conditions:
(0, , ) ( , , ) 0 y z a y z = = , y z
( , 0, ) ( , , ) 0 x z x b z = = , x z
( , , 0) ( , , ) 0 x y x y c = = , x y
The wave function at the faces of sides of a box is zero
Technique to solve: Separation of variables.
Try ( , , ) ( ) ( ) ( ) x y z X x Y x Z z =
Substitute in Schrodinger equation and divide by ( , , ) x y z (as we did for vibrating strings)

2 2 2 2 2 2
2 2 2
1 1 1
2 ( ) 2 ( ) 2 ( )
d X d Y d Z
E
m X x m Y y m Z z dx dy dz
=

This can only be true if each term itself is constant: , ,
x y z
E E E
We get 3 equations
a)
2 2
2
( )
2
x
d X
E X x
m dx
= (0) ( ) 0 X X a = =
b)
2 2
2
( )
2
y
d Y
E Y y
m dy
= (0) ( ) 0 Y Y b = =
c)
2 2
2
( )
2
z
d Z
E Z z
m dz
= (0) ( ) 0 Z Z c = =
x y z
E E E E + + =
Winter 2013 Chem 356: Introductory Quantum Mechanics

Chapter 3 Schrodinger Equation, Particle in a Box 47

This is just 3 times the 1D particle in the box equation! We know the (normalized)
solution:
2
( ) sin
k x
X x
a a
t | |
=
|
\ .

2 2
2
8
x
h k
E
m a
| |
=
|
\ .

2
( ) sin
l y
Y y
b b
t | |
=
|
\ .

2 2
2
8
y
h l
E
m b
| |
=
|
\ .

2
( ) sin
n z
Z z
c c
t | |
=
|
\ .

2 2
2
8
y
h n
E
m c
| |
=
|
\ .

Or

8
sin sin sin
x y z
y y
x x z z
n n n
n
n n
abc a b c
t
t t

| |
| | | |
=
|
| |
\ . \ .
\ .


2
2 2 2
2 2 2
8
y
x z
n
n n h
E
m a b c
| |
= + +
|
|
\ .
, , 1, 2, 3....
x y z
n n n =
Degeneracies for Cubic box
Consider the special case of a Cubic box a b c = = . Then the energy takes the form
( )
2
2 2 2
2
8
x y z
h
E n n n
ma
= + +
For each triplet , ,
x y z
n n n we get a different wave function, but different values of , ,
x y z
n n n may yield
the same energy.

Such energy levels are called degenerate. Eg.for atoms we know there are 1 s-orbital, 3 p-orbitals, 5 d-
orbitals.

Table of energies
2
2
8
h
E
ma
= ( )
, ,
x y z
n n n Degeneracy
14 (1, 2,3), (1,3, 2), (2,1,3), (2,3,1), (3,1, 2), (3, 2,1) 6
12 (2, 2, 2) 1
11 (1,1, 3), (1, 3,1), (3,1,1) 3
9 (2, 2,1), (2,1, 2)(1, 2, 2) 3
6 (1,1, 2), (1, 2,1), (2,1,1) 3
3 (1,1,1) 1