# Spectroscopy

Bohr Atomic Structure

From Classical Physics
Classical physics inability to explain atomic structure
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Unable to explain emission spectra Unable to explain blackbody radiation, photoelectric effect

Thomson’s atomic model

If an electron (-ve) is stationary, it will be pulled towards the nucleus (+ve).

Rutherford’s atomic model

If an electron is continuously orbiting the nucleus, it will emit light (energy). Soon, electron will lose its energy; and will be pulled towards the nucleus.

Rydberg suggested a complete equation for the other lines outside the visible light (infra red, ultra violet) region:

WHERE NINITIAL CAN TAKE VALUES OF N: 1, 2, 3, 4, …. AND NFINAL : N+1, N+2, N+3 …….

COMPLETE HYDROGEN LINE SPECTRUM
n1 1 2 3 4 5 n2 2,3,4, ……. 3,4,5, ……. 4,5,6, ……. 5,6,7, ……. 6,7, ………. SERIES Lymann Balmer Paschen Brackett Pfund

Bohr

Bohr’s Postulate
By combining CLASSICAL and QUANTUM theories and based on Planck’s hypothesis and information on atomic spectrum, Bohr postulated on the hydrogen atom:
1. The electron moves in circular orbit around the nucleus. 2. The electron has only a ﬁxed set of allowed orbits called stationary states. The electron in the allowed orbits have unique values. As long as an electron remains in a given orbit, its energy is constant and no energy is emitted. Allowed values for the electron is called the angular momentum are quantised in multiple values of h/2π. 3. An electron can pass only from one allowed orbit to another. During such transitions, ﬁxed discrete quantities of energy (quanta) are involved – either absorbed or emitted.

Bohr Atomic Model

Predict permissible radii of orbits for hydrogen atom
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= n2a0

where n = 1, 2, 3, …. Bohr radius, a0 = 0.53 A (53 pm)

Ionization of Hydrogen

Calculate the energy absorbed and released when excited or light emission. The change in energy when electron changes orbit;

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∆E is negative when energy/light is emitted Calculate ionization energy

Ionization of Hydrogen
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Calculate ionisation energy

Explain the line spectrum of hydrogen according to Planck equation

If,

Then,

Only applicable to hydrogen and hydrogen-like ions (He+, Li2+, Be3+… ) Unable to explain emission spectra of atoms and ions with multi–electrons No fundamental basis for the postulate of quantized angular momentum

New Quantum Mechanics
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Several failures in Bohr model Need: quantisation of energy for system initially fulﬁlled by Newtonian mechanics Need: a new approach to resolve the wave-particle conﬂict Need: to introduce the concept of quantisation of energy using acceptable basis

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Wave-Particle Duality
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Einstein (1905) suggested that light has a particle-like properties as embodied in photons (photoelectric effect). In dispersion of light by prism….. Using the following: … (by Planck) … (by Einstein)

de Broglie (1924) apply the concept and suggested the waveparticle duality with the equation:

Every object in momentum (p) will possess a wavelength (λ)
Mass (kg) 9 x 10-31 7 x 10-27 0.1 velocity (m s-1) 1 x 105 1000 20 λ (10-12 m) 7000 90 3 x 10-22

Particle Electron (gas) He atom (gas) Base ball

Wavelengths for macroscopic particles are difﬁcult to measure – too small The wave property/nature of electron was proven in an experiment involving diffraction of electron (1927)

X-RAY DIFFRACTION [WAVE]

ELECTRON DIFFRACTION [PARTICLE]

Heisenberg Uncertainty Principle

For a macroscopic particle (bullet, golf ball), its location and speed can be determined simultaneously For a microscopic and subatomic particle like electron, its location and momentum cannot be determined with light; because light are photons which will collide with the electron, displacing its position and altering its momentum

Heisenberg Uncertainty Principle

Uncertainty in position is: in momentum is:

๏Uncertainty

The resultant uncertainty in momentum and location is:

approximately: or more speciﬁcally:

Heisenberg Uncertainty Principle

The Heisenberg Uncertainty Principle states that “...it is impossible to know both the exact position and the exact velocity of an object at the same time”. However, the effect is tiny and so is only noticeable on a subatomic scale.