Wave Mechanics

Heisenbergs uncertainty principle showed that it was

impossible to know the exact path of the electron as it
moves around the nucleus as Bohr had predicted.
By mid-1920s it was apparent that Bohrs model did not
work.
Failures of classical physics made scientists realized that
new kind of mechanics was needed.
Louis De Broglie, and Erwin Schrdinger developed wave
mechanics.
Wave mechanics is the current theory used to describe the
behavior of atomic systems.
Think in terms of a probability of finding a particle within a
given space at a given time and discrete energy levels
associated with it---wave function. 1
 Probability Interpretation
Classically the intensity of an electromagnetic wave is proportional to
amplitude squared.
I E 2 nh
Intensity is proportional to the number of photons:

It follows that , for electromagnetic radiation, the probability per unit

volume of finding a particle (photon) associated with this radiation is
proportional to the square of the amplitude of the associated
electromagnetic wave.

We apply the same idea to particles probability is proportional to the

amplitude (Y) of the wave property squared.

The amplitude of the wave associated with the particle is called the
probability amplitude or the wave function Y.

2
 Probability, |Y|2
If particles are waves, whats waving? Probability
The square of the wave function determines the probability of
finding a particle at a particular position in space at a given time:

x2

The probability of the
P( x) Y ( x)
2
Y ( x) dx
2
particle being between x1
and x2 is given by:
x1

Y ( x) dx 1
2
The total probability of finding the particle
is 1. Forcing this condition on the wave

function is called normalization.

The quantity |Y|2 has an important physical interpretation:

it is related to the probability that a system can be found in
a particular region of space at a particular time.
3
Born Interpretation
The probabilistic interpretation of the wave function
was first suggested by Max Born.

In wave theory, square amplitude of wave is interpreted as intensity.

Using the same analogy, Born gave interpretation of wave function:

The probability of finding a particle in a small region of space dV

is proportional to lYl2dV, where Y is the value of wave function in the
region.

In other word, lYl2 is the probability density

4
The wave function, Y

De Broglie waves can be represented by a simple quantity

Y, called a wave function, which is a complex function of
time and position.

A particle is completely described in quantum mechanics

by the wave function.

A specific wave function for an electron is called an orbital.

The wave function can be be used to determine the energy

levels of an atomic system.

5
 The wave function, Y
The wave function is often complex-valued.

The absolute square |y|2 = y*y is always real and positive

(y* is the complete conjugate of y).

|y|2 is proportional to the probability per unit volume of finding a

particle at a given point at some instant.

The wave function contains within it all the information that can be known
about the particle.

Erwin Schrdinger proposed a wave equation that describes the manner in

which the wave function changes in space and time.

This Schrdinger Wave Equation represents a key element in quantum

mechanics.

6
 The Schrdinger Wave Equation
In 1926 Schrdinger proposed a wave equation that
describes the manner in which de Broglie matter
waves change in space and time.

The Classical Wave Equation

2u 1 2u
2 2 (1)
x 2
t
1887 1961
It can be solved by the method of separation of variables.
u(x,t) can be written as the product of a function of x and a sinusoidal
function of time:
u (x ,t ) y (x )cos t (2) Where y(x) is the spatial

substituting eq. (2) into eq. (1), we obtain: amplitude of the wave

d 2y 2
2 y (x ) 0 (3)
dx 2
7
 The total energy of a particle is the sum of its kinetic energy and
potential energy:

p2
E V (x ) (4)
2m

p 2m E V (x )
1
2
(5)

According to the de Broglie formula, the wavelength associated with

this momentum is h/p. Using Eq. (5) for p gives:

h h
(6)
p 2m E V (x ) 2
1

8
 The factor 2/ 2 in Eq. (3) can be written in terms of because = 2
and = . Putting all this together, we have

2 4 2 2 4 2 2m E V (x )
2 2 2
2

Substituting this into Eq. (3):, we get the famous Schrdinger equation:

d 2y 2m
2
2 E V (x )y (x ) 0 (7)
dx
Eq. (7) is called the time-independent Schrdinger equation. The wave
functions obtained from this equation are called stationary-state wave
functions.
Eq. (7) can be rewritten in the form:

d 2y
2
2
V (x )y (x ) Ey (x ) (8)
2m dx
9
 Eq. 7 can be written in the following form:

2
d2
2m dx 2 V y (x ) Ey (x ) (9)

2 d2
H 2
V
2m dx

Where H is the Hamiltonian energy operator for one-
dimensional systems.
2
H 2 V
For three-dimensional system: 2m
Where 2 is Laplacian Operator,
2 2 2
read as del Squared. 2
x 2
y 2
z 2

So Schrdinger equation,

in a simple form: H y Ey (10)
10
 Particle in a One-Dimensional Box
The particle is free to move over the whole
length of the molecule but not beyond!
For region I or III:
d 2y 2m I II III
dx 2 2 ( E )y 0
III
V(x)=0
Neglecting E in comparison with , we have:

d 2y 1 d 2y
y , y
dx 2
dx 2
We conclude that y is zero outside the box: x L

y I y III 0 V (x ) 0 0 x L
x 0
For region II:

The potential energy is zero, V = 0, the Schrdinger equation becomes:

d 2y 2m
2
2 Ey 0
11
dx
 One very general method for solving a differential equation is:
1) Guess a function,
2) Substitute it into the differential equation and see if it works.
We expect standing waves on physical ground so we guess waves

y A sin(kx ) B cos(kx )

What are A and B ? They are arbitrary constants and can be

determined by applying boundary conditions.
Since a wave function must be continuous (Boundary conditions):
y (0) y (L ) 0
Cosine is not zero at x = 0,
0 A sin k 0 B cos k 0
0 A 0B 1
B 0
y II A sin kx 12
Sine is zero at x = 0, so at x = L we need:

A sin kL 0

If A = 0, trivial solution is obtained, so sinkL must be equal to 0.

sinkL = 0 only when kL = n for n = 0,1,2,
hence k = n/L

n x
y II A sin
L

13
Using Borns interpretation: Normalization condition

y dx 1
2

0 L

y dx y dx y 1
2 2 2
I II III dx
0 L
L
0 y dx 0 1
2
II
0

n x
L
A sin
2
dx 2
1
0
L
14
 From cos (A+B) = cosAcosB - sinAsinB
cos2x = cosxcosx - sinxsinx
= cos2x - sin2x
= (1-sin2x) - sin2x
cos2x = 1- 2sin2x
sin2x = (1 cos2x)/2

n x 1 cos 2 n x
L d n x L
L L

0 sin L dx
2

0
2 L n
1
L 1 n x
( )
L L
1
d cos n x d 2 n x
n 2 0 L 20 L L 2
L 1 n x L 1 2n x L
L

n 2 L 0

0
d sin
4 L 0


15
 L n 1 L
(1 0 ) ( sin 2 n sin 0 )
n 2 4 2
2
n x
L
L 2
A sin
2
dx A 2
1 A
0
L 2 L
If n=0 E=0 so y=0,
2 n x which means that
y n (x ) sin the particle does not
L L exist in the n=0 state

2
k2 h 2 n 2 2 h 2 n 2
En n 1, 2,3,....
2m 8 m L
2 2
8mL2

The energy of the particle is quantized.

The quantization arises from the
boundary conditions.
16
 The lowest energy is achieved when n = 1, and equal to h2/8mL2.
Note that E0 = 0 is not a possible energy level.
The lowest energy is non-zero called zero-point energy.
Excitation or transition to adjacent wall could be calculated as:

E En 1 En

h2
8mL2
(n 1)
2
n 2

h2

8mL2
n2
2 n 1 n 2

h2
( 2n 1)
8mL2

17
 Probability Density for a particle in a box

The probability of observing the

particle between x and x + dx in
each state is:

2 2 n
y ( x) sin
2
x
L L
when n is small, y 2 ( x) non uniform
as n gets large, y 2 ( x) more uniform

Quantum result classical prediction

at high quantum number

The concept of energy levels, as first discussed

in the Bohr model, has surfaced in a natural way
by using waves.
18
Operators
Classical mechanical quantities are represented by linear
Operators in Quantum Mechanics.

The one-dimensional time-independent Schrdinger equation can

be written in the form:
2
d2

2m dx 2 V ( x ) y (x ) Ey (x )

The entity in the brackets is an energy operator which operates on the
wave function giving the wave function back again multiplied by the
allowed values of energy.
An operator is a rule (set of instructions) for changing some function
or vector into another one.
Use carrot or circumflex, ^, to denote operators.
d , so the rule is take the derivative w.r.t. x
For example: Let D
dx

19
 Operators may be combined with each other:

Addition: (A B )f (x ) Af (x ) Bf (x )

Equality: A f (x ) B f (x ) for all f (x ) then A B

Product:
Let A B f (x ) A Bf (x ) , so B acts first.


In general: A B B A

Example:
define x multiply by x

then D x x D
d
since D x f (x ) xf (x ) f (x ) xf (x )
dx

d
and x D f (x ) x f (x ) xf ( x )
dx
so operators do not commute 20

Identity: 1 so that 1f (x ) f (x ) (no change)

Null: 0 so that 0 f (x ) 0

Association: A (B C ) ( A B )C

Since we do not have the commutative laws of multiplication we define:

A , B A B B A The commutator of A and B

A , B A B B A The anticommutator of A and B

If A , B 0 we say A and B commute


If A , B 0 we say A and B anticommute

so , is also an operator
21
Linear Operator:
is defined as: A f (x ) g (x ) A f (x ) A g (x )

and: A cf (x ) c A f (x ),
where c is a scalar constant.

Notice x and D were linear operators.
a "take the square root" operator is not.

Distributive Law:
A B C AC B C

addition over multiplication

Dr. Sabry El-Taher 22

 Operator shorthand is used for Schrdinger equation:

2
d 2


2m dx 2 V ( x ) y (x ) Ey (x )
kinetic operator potential operator

Hamiltonian operator

H y (x ) Ey (x )

Notice that the effect of H is to give us the energy times y (x).
The energy is a constant scalar.

For an operator A if:

A f (x ) kf (x )

k is an eigenvalue of A and f(x) is an eigenfunction of A

23
 In general: we wish to find the eigenvalues and eigenfunctions
of the various Hamiltonian operators of Quantum Chemistry
to determine: Electron Density (y*y ), Spectra ( Ei ), etc.

In Classical Mechanics: the Hamiltonian

function was
Px2 Sum of the kinetic and potential
H V (x ) Energies of the system
2m
In Quantum Mechanics:

H H quantum
classical

2
px p x2
V (x ) +V (x )
2m 2m
2 d2
d
= 2
V (x ), since p x
2m dx i dx

24