QUANTUM THEORY

Structure and Chemical Bonding

Sudirman, M.Si
 THE FAILURES OF CLASSICAL PHYSICS
• Black-body radiation

Lord Rayleigh and James

Jeans
∞ Unfortunately, Although the Rayleigh–Jeans law
Ε(𝑇) න 𝜌 𝜆, 𝑇 𝑑𝜆 is quite successful at long wavelengths (low
0
frequencies),it fails badly at short wavelengths
(high frequencies). Thus, as λ decreases, ρ
8𝜋𝑘𝑇
𝜌= increases without going through a maximum
𝜆4
 QUANTUM MECHANIC SOLUTION

• The Plank Distribution

the German physicist Max Planck found that he could
account for the experimental observations by proposing
that the energy of each electromagnetic oscillator is
limited to discrete values and cannot be varied arbitrarily.

E = nh n = 0, 1, 2, . . .

8𝜋ℎ𝑐
𝜌= ℎ𝑐ൗ
𝜆5 𝑒 𝜆𝑘𝑇 −1
 THE FAILURES OF CLASSICAL PHYSICS

• Heat capacities
Pierre-Louis Dulong and AlexisTherese Petit
𝑈𝑚 = 3𝑁𝐴 𝑘𝑇 = 3𝑅𝑇
𝜕𝑈𝑚 Dulong
𝐶𝑣 = = 3𝑅 = 24.9 𝐽 𝐾 −1 𝑚𝑜𝑙 −1 Petit’s Law
𝜕𝑇 𝑉

Unfortunately, significant deviations from their law

were observed when advances in refrigeration
techniques made it possible to measure heat
capacities at low temperatures. It was found that the
molar heat capacities of all monatomic solids are
lower than 3R at low temperatures, and that the
values approach zero as T=>0
 QUANTUM MECHANIC SOLUTION

• Single frequency

Albert Einstein
3𝑁𝐴 ℎ𝑣
𝑈𝑚 = ℎ𝑣ൗ
𝑒 𝑘𝑇 −1
2
2 𝜃𝐸ൗ
𝜃𝐸 𝑒 2𝑇
𝐶𝑉,𝑚 = 3𝑅𝑓𝐸 𝑓𝐸 = 𝜃𝐸ൗ
𝑇 𝑒 𝑇 −1
• Range frequency
Debye Huckle
3 𝜃𝐷ൗ
𝜃𝐸 𝑇 𝑥 4𝑒 𝑥
𝐶𝑉,𝑚 = 3𝑅𝑓𝐷 𝑓𝐷 = න 𝑑𝑥
𝑇 0 𝑒𝑥 − 1 2
 THE FAILURES OF CLASSICAL PHYSICS

• Atomic and Molecular Spektra

The record of light intensity transmitted or scattered by a molecule as a function of frequency, wavelength or
wavenumber is called its spectrum (from the Latin word for appearance)

∆𝐸 = ℎ𝑣
Bohr frequency
condition
 WAVE-PARTICLE DUALITY
1
• The particle character of electromagnetic radiation 𝑚𝑒 𝑣 2 = ℎ𝑣 − Φ
2
The observation that electromagnetic
radiation of frequency  can possess
only the energies 0, h, 2 h, 3 h...

suggests (and at this stage it is only a

suggestion) that it can be thought of
as consisting of 0, 1, 2,...particles, each
particle having an energy h.

These particles of electromagnetic

radiation are now called photons

Experimental evidence for their

existence comes from the
measurement of the energies of Self test: Explanation of
electrons produced in the photoelectric effect
photoelectric effect
 YOUR TURN
• Calculate the number of photons emitted by a 100 W yellow lamp in 1.0 s.
Take the wavelength of yellow light as 560 nm and assume 100 per cent
efficiency.
• How many photons does a monochromatic (single frequency) infrared
rangefinder of power 1 mW ? nd wavelength 1000 nm emit in 0.1 s?
 WAVE-PARTICLE DUALITY

• The wave character of particles

The crucial experiment was performed by

the American physicists Clinton Davisson
and Lester Germer, who observed the
diffraction of electrons by a crystal.

Some progress towards coordinating these

properties had already been made by the
French physicist Louis de Broglie when, in
1924, he suggested that any particle, not only
photons, travelling with a linear momentum p
= mv, should have in some sense a
wavelength given by the de Broglie relation:

ℎ
𝜆=
𝑝
 YOUR TURN
• Estimate the wavelength of electrons that have been accelerated from rest
through a potential difference of 40 kV!
• Calculate the wavelength of (a) a neutron with a translational kinetic energy
equal to kT at 300 K, (b) a tennis ball of mass 57 g travelling at 80 km/h
 THE HEISENBERG UNCERTAINTY PRINCIPLE

• It is impossible to specify simultaneously, with arbitrary precision, both the

momentum and the position of a particle.

1
Δ𝑝Δ𝑥 ≥ ℏ
2

Self Test
Suppose the speed of a projectile of mass 1.0 g is known to
within 1 µm/s Calculate the minimum uncertainty in its
position.
 THE SCHRÖDINGER EQUATION
Operator, eigenvalues and eigenfunction

෡ = 𝐸Ψ
𝐻Ψ Eigenvalue equation
Operator Hamiltonian

Eigenvalue

Eigenfunction