Electronic Structure of Atoms

From Classical Theory

To Quantum Mechanic
 Overview
๏ The classical electromagnetic and light theorem

๏ How an electron can be described in terms of quantum numbers

and its orbitals

๏ Experiments involved

1. Atomic Spectrum

2. Black Body Radiation

3. Photoelectric Effect

4. Electron Diffraction
The Classical Theory
On Electromagnetic and Light
 What is A Wave?

Wave is an interference which can transmit energy

through matter or space
Examples and Components
๏ Waves
๏ through matter: sound, ocean wave
๏ through space: electromagnetic waves
๏ Wavelength (λ), Frequency (ν), Amplitude (y)
 Continuous Spectrum

White light when passed through a prism will be refracted

and dispersed into a continuous spectrum of colors
Electromagnet Wave
 Classical EM Theory
Electromagnetic (EM) radiation is a form of energy transmission
of electric and magnetic fields which propagate as waves
through empty space or through a medium e.g. glass
 Electromagnetic Wave
๏ Very often to explain optical phenomena
๏ Frequency (ν) in unit Hertz (Hz or s-1)
๏ Wavelength (λ) in unit meters [m, cm (10-2 m), μm (10-6 m),
nm (10-9 m), pm (10-12 m), etc.]
๏ The speed of a wave travels is the product of the two properties
๏ Speed of light in vacuum, c = ν ⋅ λ ; ~ 3 x 108 ms-1

๏ c=λ⋅ν λ=c/ν γ=c/λ

๏ However, this theory cannot explain radiation from a heated solid.

What is heated solid radiations?

 Radiation from Heated Solid
๏ Light emitted from a discharge tube containing an element e.g.
hydrogen or helium
๏ Light refracted by a prism to produce an atomic line spectrum
๏ Available technique since 1859
 Wrong But Right…

๏ This spectrum cannot be explained until early 20th century.

๏ However, Balmer (1885) suggested an equation which can be used
to calculate the positions of the lines of the hydrogen spectrum in
the region of visible light:

๏ where n = 3, 4, 5, 6, ...
Series of Spectrum
 Other Spectra

Eventually, this equation still puzzling especially

to construct an atom model
 The Failure of
Classical Theory
Max Planck Explanation
 Blackbody Radiation
Blackbodies above 700 K begin to produce radiation at visible
wavelengths starting at red, going through orange, yellow, green
and ending up at blue as the temperature increases.
 Blackbody Radiation
๏ A blackbody is an object that absorbs all
electromagnetic radiation that falls onto it.
๏ No radiation passes through it and none is
reflected, yet it theoretically radiates every
possible wavelength of energy.
๏ The amount and type of electromagnetic
radiation they emit is directly related to their
temperature.
๏ Blackbodies below around 700 K produce
very little radiation at visible wavelengths
and appear black (hence the name).
 Rayleigh-Jeans Law
๏ dΕ = ρdλ , ρ = (8πkT) / λ4

๏ Derived from equipartition

principle
๏ It is only true at long
wavelength (low frequencies)
๏ At short wavelengths (UV, X-
ray, γ-ray), the energy
predicted is very large -
ultraviolet catastrophe
 What Planck Said?
๏ Planck’s Hypothesis (1900)
1. Cannot have any arbitrary energy but
only certain selected energy
2. Energy of the radiation, E is
proportional to the frequency, v

๏ Energy, E = nhv
n : positive integer,
v : the oscillator frequency
h : Planck’s constant (6.626 x 10-34 Js)
 Planck Hypothesis
๏ This energy unit is called quanta
๏ From the spectral density and E = nhv

๏ dE = ρdλ , ρ = 8πhc ⁄ (λ5 (ehc/λkT - 1)

๏ The equation fit well with at all

wavelengths
๏ His idea was rejected
๏ This was the beginning of quantum
mechanics