Electronic Structure of Atoms

From Classical Theory To Quantum Mechanic

Overview
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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
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matter: sound, ocean wave 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
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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.]

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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

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Wrong But Right…

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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, Xray, 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
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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

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