QUANTUM THEORY

I. Review of Classical Mechanics

Re: Atkins (8
th
Ed.) Appendix 3
Atkins (9
th
Ed.) Chapter 7 -
Further information
Classical Mechanics
Cannot explain some well-known
phenomena observed experimentally near
the end of the 19
th
Century/beginning of the
20
th
Century:
Blackbody radiation
Photoelectric effect
Heat capacities of solids
Compton effect
Electron scattering
Atomic and molecular spectra
Classical Mechanics
Cannot account for the behavior of
very small particles (atoms and
molecules).
Quantum theory: a technique of
calculation at the microscopic level,
for the study of the behavior of
individual atoms and molecules.
Central Ideas in Classical
Mechanics
Some key expressions
Total energy:
Linear momentum:
Speed:
V E E E E
K P K
+ + =
mv p =
m
p
dt
dx
v = =
m
p
v m E
K
2 2
1
2
2
=
( )
2 / 1
2 / 1
) ( 2 2
(

=
m
V E
m
mE
v
K
As a function of
energy:
Newtons second law:
Acceleration:
a m
dt
x d
m
dt
mv d
dt
dp
F = = =
2
2
) (
2
2
dt
x d
a =
Classical Mechanics is based on Newtons
laws of motion, and predicts the response
of objects to FORCES.
Rotational analogy
angular
velocity
r radius
angle swept in
radians
Length of the arc
r

r
Translation Rotation
Mass Moment of inertia
Velocity Angular velocity
Linear momentum Angular momentum
Kinetic energy
Force Torque
2
mr I =
r v / =
mv p =
v
m
I r m mvr pr J = = = =
2
m
p
mv T E
K
2 2
1
) (
2
2
= =
I
J
I R E
K
2 2
1
) (
2
2
= =
dt
dp
F =
dt
dJ
T =
Free particle
Total energy: E = E
K
+ E
P
E
K
+ V
For the free particle: V = const (say 0)
E = E
K
=const
1
st
order ODE:
Solution:
2 / 1
2
|

\
|
=
m
E
dt
dx
Const
( )
0 0
0
0
0
2 / 1
) (
) (
/ 2 ) (
x t v t x
x t
m
p
t x
x t m E t x
+ =
+ =
+ = Uniform
motion with
constant initial
velocity v
0
Harmonic Oscillator
Particle disturbed
from its rest position
and experiences a
RESTORING FORCE
whose magnitude is
directly proportional
to the displacement. x = r r
eq
r
eq
r
x k F =
k force constant (in N/m)
F
r
Properties
Equation of motion:
Potential energy:
Total energy:
x k
dt
r d
m =
2
2
2
0 0
2
1
. x k dx x k dx F E P
x x

= = =
2 2
2
1
2
1
. .
x k v m
E P E K E
+ =
+ =
2
.
2
) (
2
1
2
1
eq
r r k x k V = =
Solution
2
nd
Order ODE
General solution:
Solution for HO: x = A sin t
A amplitude of the motion
angular frequency
0
2
2
=
|

\
|
+ x
m
k
dt
x d

2
t B t A x cos sin + =
Properties of the oscillator
The position varies harmonically with time.
Momentum is least when the particle is at
maximum displacement.
Period: T = 2/ (s)
Frequency: s
1
(Hz)

2
1
= =
T
2.5 5 7.5 10 12.5 15 17.5
-1
-0.5
0.5
1
T
T
x (t)
t
Momentum: p = mv = m A cos t
Potential energy:
Total energy:
Analogy with a vibrating chemical
bond:
2
2
1
x k V =
2
2
1
A k E =
Typically, k = 500-800 N/m
Properties of waves
Wavelength distance
between two peaks or
troughs. ()
Frequency number
of cycles that pass
through a given point
in space per unit time.
()
Hz
) / (
wavelength
speed
ycle distance/c
second travelled/ distance
1
or s
m
s m

= =
=

v
Wavenumber:

1
~
=
The electromagnetic field
A great deal of information on molecular structure is
revealed by the interaction of radiation with matter.
Radiation emission and transmission of energy in
the form of waves.
Light electromagnetic radiation (how energy
travels through space).
The electromagnetic field is an oscillating electric
and magnetic disturbance that spreads as a
harmonic wave through vacuum (empty space).
Magnetic and Electric fields
For all electromagnetic radiation:
speed c = 2.998 10
8
m/s
The electromagnetic spectrum
Features of electromagnetic
radiation
Oscillating electric field:
Oscillating magnetic field:
If = or , the peaks of one wave
coincide with the troughs of the other the
waves are out-of-phase: destructive
interference.
If = 0, the peaks and troughs of the two
waves coincide together the waves go in
phase: constructive interference.
] ) / 2 ( 2 cos[ ) , (
0
+ = x t E t x E
] ) / 2 ( 2 cos[ ) , (
0
+ = x t B t x B
We can show that E(x,t) and B (x,t)
satisfy the following two equations:
where (x,t) is either E(x,t) or B (x,t).

2
2
2
2
4
=

2 2
2
2
4 =

t
Constructive and destructive
interference
NO spot
In between
Partial cancellation
Produce Dull spot
Diffraction pattern of an NaCl crystal