INTRODUCTION TO QUANTUM MECHANICS

CLASSICAL MECHANICS QUANTUM MECHANICS

It is a branch of physics that studies It is another branch of physics that
the motion and behavior of objects on deals with the behavior of sub-atomic
a bigger scale. particle.
It failed at explaining the motion of
everyday objects and planets when it
was applied to particles as small as
electrons.
It predicts a precise trajectory for
particles, with precisely specified
locations and momenta at each instant
Allows the translational, rotational, and
vibrational modes of motion to be
excited to any energy simply by
controlling the forces that are applied.
In classical physics, light is described
as electromagnetic radiation.

Electromagnetic field

- An oscillating electric and magnetic disturbance that spreads as a harmonic wave

through empty space, the vacuum.
- Has two components: Electric Field & Magnetic Field

WAVE

- The wave travels at a constant speed called the speed of light, c, which is about 3
108 m s1

WAVELENGTH,

- distance between the neighboring peaks

of the wave

FREQUENCY (v)

- the number of times per second at which its displacement at a fixed point returns to its
original value

- Frequency is the measure of number of cycle a wave completes in one second. The
wavelength of a wave is inversely proportional to the frequency of the wave and is
directly proportional to its velocity.

- The frequency is measured in hertz, where 1 Hz = 1 s1

WAVENUMBER

- Defined as spatial wavelength and it is inversely proportional to the wavelength.

- Wavenumbers are normally reported in reciprocal centimeters (cm1).
 c=v

Where c = the speed of light (cm/s)

V = frequency (Hz)

= wavelength (cm)

1
W=

Where W = wavenumber (cm-1)

= wavelength (cm)

The Electromagnetic Spectrum

- the description and classification of the electromagnetic field according to its frequency
and wavelength

PLANCKS QUANTUM THEORY

Basically states that energy is always emitted or absorbed in discrete units, called
quanta

E=h, where h is Planck's constant (6.62606957(29) x 10-34 J s), is the frequency, and
E is energy of an electromagnetic wave.

Energy is always emitted or absorbed as a whole number multiple of h (2hv, 3hv)

Karl Ernst Ludwig & Marx Planck - father of Quantum Theory

Planck postulated that the energy of light is proportional to the frequency, and the
constant that relates them is known as Planck's constant (h). His work led to Albert
Einstein determining that light exists in discrete quanta of energy, or photons.

BLACKBODY

- name given to a theoretical ideal emitter

- an object capable of absorbing and emitting all wavelengths of radiation equally
- may be successfully approximated by a small opening into a heated cavity
ENERGY DISTRIBUTION

The energy density increases in the

region of shorter wavelengths as the
temperature is raised, and the peak
shifts to shorter wavelengths. The total
energy density (the area under the
curve) increases as the temperature is
increased.

BLACKBODY RADIATION

- The type of electromagnetic radiation within or surrounding a body in thermodynamic

equilibrium with its environment, or emitted by a black body (an opaque and non-
reflective body), assumed to be held at constant, uniform temperature.

Physicist Lord Rayleigh

- Thought of the electromagnetic field as a collection of oscillators of all possible

frequencies

Ultraviolet Catastrophe

- Implies that a large amount of energy is radiated in the high-frequency region of the
electromagnetic spectrum

RayleighJeans Law

- Predicts an infinite energy density at short wavelengths. This approach to infinity is

called the ultraviolet catastrophe.

dE=d

8 kT
=
4

Where = density of states,

dE = energy density

k = Boltzmanns constant (k = 1.381 x 10-23 J/K).

Planck Distribution

- This expression fits the experimental curve very well at all wavelengths.

dE=d

8 hc
=
( e hc/ kT 1 )
5

Where = density of states,

k = Boltzmanns constant (k = 1.381 x 10-23 J/K).

h = Plancks constant (h = 6.626 x 10-34 Js.)

Dulong and Petit Law

- Pierre-Louis Dulong and Alexis-Thrse Petit determined the heat capacities of a

number of monatomic solids (25 J mol-1 K-1)
- unfortunately, significant deviations from their law were observed when advances in
refrigeration techniques made it possible to measure heat capacities at low temperatures

C v =3 R

Where R is the gas constant

Einstein Formula

CV ,m =3 Rf

2 2
E e / 2 T
( )( )
E

f= /T
T e 1E

Einstein Temperature

- a way of expressing the frequency of oscillation of the atoms as a temperature; a high

frequency corresponds to a high Einstein temperature.
E=hv /k

Debye Formula

CV ,m =3 Rf

3 D /T
T x4 ex
f =3
D( ) (e 1) dx
0
x 2

Debye Temperature

- The poor fit arises from Einsteins assumption that all the atoms oscillate with the same
frequency, whereas in fact they oscillate over a range of frequencies from zero up to a
maximum value.

D=h v D / k

Spectroscopy
- the detection and analysis of the electromagnetic radiation absorbed, emitted, or
scattered by a substance
Spectrum
- The record of the intensity of light intensity transmitted or scattered by a molecule as a
function of frequency, wavelength, or wavenumber

References:
Atkins, P. and de Paula, J. (2006). Atkins Physical Chemistry. 8th edition. pp. 243-249