Fall

2014 Chem 356: Introductory Quantum Mechanics

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 .................................................................................................... 42
Useful integrals for particle in the box ..................................................................................... 44
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 p =

e ikx

Generalization to 3 dimensional wave

! !
i
k
e i x

2

k

p=

h
k = !k
2

!
!
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

Choose solution with particular =

2 u
1 2 u
=

x 2 V 2 t 2

u(x,t) = (x)cos( t)

34

Fall 2014 Chem 356: Introductory Quantum Mechanics

d 2 2
+
( x) = 0
dx 2 V 2

= 2 v

= V ,

2 2
=
=
(nu) frequency ; V

velocity

d 2 4 2
+ 2 (x) = 0
dx 2

4 2 4 2 2 p
= 2 p =
!
2
h

h
=
p

Now substitute p 2 :

! 2

2
+ p 2 (x) = 0
dx 2
Let V = V(x) indicate potential:

p2
+ V = E
2m

2
2
2
! p

+
(x) = 0
2m x 2 2m

! 2 2
+ ( E V ) (x) = 0
2m x 2

! 2 2
+ V (x) (x)
2m x 2

H (x)









We obtain a differential equation for function ( x)





H (x) = E (x)

Or

E (x) =

Summarizing:

1)

2

p (x) = !
x 2
2

E is a constant, the energy

H is operator that acts on a function.

(using de Broglie + classical wave equation)

Chapter 3 Schrodinger Equation, Particle in a Box 35

Fall 2014 Chem 356: Introductory Quantum Mechanics

2) Substitute p 2 = 2m( E V ( x))

h 2
+ V ( x) ( x) = E ( x)
2m x 2

H ( x) = E ( x)
2

p 2
H =
+ V (x)
2m

energy operator (see later)

We need to discuss 2 mathematical items

p , H , p 2 .?

a) Operators

b) Eigenvalue equations
H = E
!
p = p

!
E, p : numbers

Operators will be indicated by ^ hat or carot

Linear Operators
(in 1 dimension first)

( x) = g ( x)
Af

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

d2

dx 2
d2

d
2 + 2 + 3
dx
dx

d
x
dx
d
x
dx
d
i!
dx
2
2
! d

+
V
(x)
2m dx 2

( x) = g ( x)
Af

f ( x)
2x

x 3

6 x + 6 x 2 + 3x3

x 2
x 2

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

e ikx

!keikx

cos(kx)

!2k 2

+
V
(x)
2m
cos(kx)

Chapter 3 Schrodinger Equation, Particle in a Box 36

Fall 2014 Chem 356: Introductory Quantum Mechanics

The operators we consider are linear operators:

A (c1 f1 ( x) + c2 f 2 ( x))

( x) + c Af
( x)
= c1 Af
1
2
2

Where c1 , c2 are (complex) constants

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

( f ( x))2

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

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







Not linear therefore
We can act with operators in sequence
( x) = A ( Bf
( x))





ABf

In general:

Example

( x) BAf
( x)
ABf

d
A = x , B =
dx
df
d

x f ( x) = x
dx
dx
d
df
d
x f ( x) = ( xf ( x)) = f ( x) + x
dx
dx
dx

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

BA
= 0
AB
A and B commute, the order does not
[ A , B ] = 0

matter. This will play an important role later on.

Eigenvalue equations (by example)





A (x) = a (x)

Acting with A on a function yields the same function multiplied by a constant.

Example:

i!

ikx
e = (i!)(ik)eikx
x

= !keikx
Chapter 3 Schrodinger Equation, Particle in a Box 37

Fall 2014 Chem 356: Introductory Quantum Mechanics

h 2 ikx
=

e
2

interpretation: =

We say

p x = i!

p x eikx = px eikx

eikx = peikx

periodic with period

eikx = e

Number

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

p x = i!

!k =

d
, with eigenvalue
dx

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

Consider kinetic energy operator
2

i!
2

p
!2 d 2
=
=

2m
2m
2m dx 2
Eigenfunctions of Kinetic energy:

Or

Also

!2 d 2
!2 2

cos(ax) =
a cos(ax)
2m dx 2
2m

! 2 d 2 ax
!2a2
< 0 !!
(if a is real)
e
=

2m dx 2
2m



Not physical

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

eiax

Constant Eigenvalue

! 2 2 iax
a e
2m
Chapter 3 Schrodinger Equation, Particle in a Box 38

Fall 2014 Chem 356: Introductory Quantum Mechanics

Or Hamiltonian operator:

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

H ( x) = E ( x)

: particle described by eigenfunction ( x) has the definite energy E , (to be discussed

in more detail in chapter 4)



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 < x < a
V ( x) = 0

V ( x) =

elsewhere

We wish to solve

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




E is a Constant

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

We also wish ( x) to be continuous:

Inside the box we have V = 0

Chapter 3 Schrodinger Equation, Particle in a Box 39

Fall 2014 Chem 356: Introductory Quantum Mechanics

! 2 d 2
= E (x)
2m dx 2


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

We considered before this equation




General Solution:
c sin(kx) + b cos(kx)

n
, n = 1, 2,3
a
Any c , c not equal to 0



n x
( x) = c sin

a

= 0

x = 0

b = 0

x = a c sin(ka) = 0

E=

!2k 2

2m

k=

! 2 n2 2 h2 n2
=

2ma 2
8ma 2

E =

n = 1, 2,3.....

-
-

Quantization: Combination of wave equation + Boundary conditions

n = 1, 2, 3 also possible, but yields same solutions

n x
n x

c sin
= c sin
a
a
c can be anything (still)

For any operator A , with eigenfunction (x)

( x) = cA ( x)
Ac

= 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 :

Chapter 3 Schrodinger Equation, Particle in a Box 40

Fall 2014 Chem 356: Introductory Quantum Mechanics

p( x) 0

p( x)dx = 1

x =

xp( x)dx etc.

The absolute square of the wave function ( 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

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

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

f ( x) , g ( x) real

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

= f (x) + g(x)
2

(real always)

Also ( x) > 0

Moreover (we should impose):

everywhere

Probability distribution

( x)

dx 1

Normalization

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

Particle in the box (later)

2
n x
sin

a
a

n ( x) =

Further Interpretation
xhigh

( x) ( x)dx
*

xlow

Probability to find particle between xlow and xhigh

And
Chapter 3 Schrodinger Equation, Particle in a Box 41

Fall 2014 Chem 356: Introductory Quantum Mechanics

x =

x * (x) (x) dx =

(x)x (x) dx

Determination of Constant C

We will impose that the wave functions are normalized

( x) ( x)dx 1

For reasons discussed before

* ( x) : complex conjugate of functions

( x) = f ( x) + ig ( x)

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

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

= f ( x) + g ( x)

= ( x)

If ( x) is real then ( x) = ( x)2

f ( x) , g ( x) real

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

0 everywhere
2

Consider particle in the box wave functions:

n x

a
0, elsewhere

n ( x) = Cn sin

0 x a

n x
( x) dx = 0 Cn sin a dx
a

= Cn 2 = 1
2
a

2 i
e would work too.
a
We can always choose the function ( x) to be normalized (for meaningful wave

Choose Cn =

2

a

Simplest,

functions)


A physically meaningful wave function would be normalized
If A ( x) = a ( x) eigenfunction of A , eigenvalue a
Chapter 3 Schrodinger Equation, Particle in a Box 42

Fall 2014 Chem 356: Introductory Quantum Mechanics

Then

And:

* ( x) A ( x)

= * ( x)a ( x) = a * ( x) ( x)

( x) A ( x) dx

= a * ( x) ( x)dx

= a 1

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

IF ( x) is normalized

average value A = a

If ( x) is not an eigenfunction of A , then many values could be obtained if A is

measured. The average value would be A (much more discussion later)

One more definition:

( A A )

: The standard deviation from the average. The spread of the

measured values

( A A )( A A )

= A 2 2 A A + A

= A 2 2 A A + A

= A 2 A

= A 2

Depends on wave function ( x)

Chapter 3 Schrodinger Equation, Particle in a Box 43

Fall 2014 Chem 356: Introductory Quantum Mechanics

Using definition: A 2 = * (x) A 2 (x) dx

Useful integrals for particle in the box

sin

bx dx =

x sin 2bx

2
4b
x 2 x sin 2bx cos 2bx

4
4b
8b2

2
x sin bx dx =

2
2
x sin bx dx =

Definite Integrals (Most important). Use b =

a

x3 x2
1
cos 2bx
3 sin 2bx x

6 4b 8b
4b2

n x
a
dx =
a
2

sin

n x
a2
0 x sin a dx = 4

n
n
; bx x=a =
a = n
a
a

2
2
x sin
0

sin
0

n x
a3
a3
dx =
2 2
a
6 4n

n x
m x
cos
dx = 0, n,m integers
a
a

Demonstration of Uncertainty Principle

Using the above integrals, we can calculate the following
n x
a) Normalize n = Cn sin

a
2

n x

2 a
Cn 2 sin
1
dx = Cn
a
2

0
a

Normalized particle in the box eigen states:

Cn = C =

2

a

2
n x
sin

a
a

b) Calculate x for normalized n ( x) :

Chapter 3 Schrodinger Equation, Particle in a Box 44

Fall 2014 Chem 356: Introductory Quantum Mechanics

2
n x
n x
x = sin
x sin
dx
a0
a
a
a

2 a2 a

=
a 4 2

center of the box

c) Calculate x 2

2
n x 2
n x
sin
x sin
dx

a0
a
a
a

x2 =
=

2 a3
a3
2 2
a 6 4n

a2
a2

=

2 2
3 2n

d) Standard deviation in x :
2

x 2 = x 2 x
2

2 2

a2
a2
a2
a2
a
a n
=
2 2 =
2 2 =
2

3 2n
12 2n
2
2 n 3

e)

2
n x
d
n x
Px = sin
i! sin
dx

a0
a
dx
a
a

2
n
n x
n x
= i! sin
cos
dx = 0
a
a 0
a
a

f)

2
x

a
2
n x 2 d 2
n x
= sin
!
sin

2

a0
a
a
dx
2

2
n2 2 n x
dx
= ! 2 2 sin
a
a
a 0

! 2 n2 2 h2 n2
=

=
a2
4a 2
hn
( Px ) =

2a

a

2

( = 2mEn , of course!)

We can test the Heisenberg Uncertainty Principle
1

2 n2
2 hn
x p =

2
2 n 3
2a

2
! 2 n2
=
2
2 3

>

!

2

Chapter 3 Schrodinger Equation, Particle in a Box 45

Fall 2014 Chem 356: Introductory Quantum Mechanics

Note 1: x

a
12

as n is the same as uncertainty in uniform distribution:

x =

2 a

1x
a 2

a

2

Px

11 3
1
=
x = a 2
a3 0 3
a2 a2 a2

=
uniform
3
4 12
grows with n. Why?
=

Pn = (2mEn ) =

n2 2 ! 2

a2

Spiked distribution
Large Uncertainty
represents the classical limit of particle of
bouncing back and forth in the box

This
energy En

Note 2: x , x 2 , Px , Px 2 Can be calculated for any wave function

for example: ( x) = Cx(a x) also satisfies the boundary conditions

Particle in a 3 dimensional box

Consider rectangular box of length a, b, c
Chapter 3 Schrodinger Equation, Particle in a Box 46

Fall 2014 Chem 356: Introductory Quantum Mechanics

3D Schrodinger Equation:

! 2 2
2
2

+
+
(x, y, z) = E ( x, y, z )
2m dx 2 dy 2 dz 2

Boundary Conditions:
(0, y, z ) = (a, y, z ) = 0
( x,0, z ) = ( x, b, z ) = 0
( x, y,0) = ( x, y, c) = 0

y, z
x, z
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 1 d 2 X ! 2 1 d 2Y ! 2 1 d 2 Z

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

This can only be true if each term itself is constant: Ex , E y , Ez

We get 3 equations

h2 d 2 X
= Ex X ( x)
2m dx 2
h2 d 2Y
b)
= E y Y ( y )
2m dy 2
a)

c)

h2 d 2 Z
= Ez Z ( z )
2m dz 2
Ex + E y + Ez = E

X (0) = X (a) = 0
Y (0) = Y (b) = 0
Z (0) = Z (c) = 0

This is just 3 times the 1D particle in the box equation! We know the
(normalized) solution:

X ( x) =

2
k x
sin

a
a

Ex =

h2 k 2

8m a 2

Y ( y) =

2
l y
sin

b
b

Ey =

h2 l 2

8m b2

2
n z
Z ( z) =
sin

c
c

h2 n2
Ey =

8m c 2

Or
Chapter 3 Schrodinger Equation, Particle in a Box 47

Fall 2014 Chem 356: Introductory Quantum Mechanics

n n n =
x y z

8
n
sin x x
abc
a

ny y

sin b

nz z
sin
c

2
nz 2
h 2 nx 2 n y

E=
+ 2 + 2
nx , n y , nz = 1, 2,3....

8m a 2
b
c
Degeneracies for Cubic box
Consider the special case of a Cubic box a = b = c . Then the energy takes the form

h2
E=
n 2 + ny 2 + nz 2 )
2 ( x
8ma
For each triplet nx , n y , nz we get a different wave function, but different values of nx , n y , nz 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

E=

h2

8ma 2
14
12
11
9
6
3

( n , n , n )

Degeneracy

(1, 2,3),(1,3, 2),(2,1,3),(2,3,1),(3,1, 2), (3, 2,1)

(2, 2, 2)
(1,1,3),(1,3,1),(3,1,1)
(2, 2,1),(2,1, 2)(1, 2, 2)
(1,1, 2), (1, 2,1), (2,1,1)
(1,1,1)

6
1
3
3
3
1

Chapter 3 Schrodinger Equation, Particle in a Box 48