Spectroscopy

Bohr Atomic Structure

 From Classical Physics
Classical physics inability to explain atomic structure
๏ 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 n2 SERIES
1 2,3,4, ……. Lymann
2 3,4,5, ……. Balmer
3 4,5,6, ……. Paschen
4 5,6,7, ……. Brackett
5 6,7, ………. 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

๏ rn = 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;

๏ ∆E is negative when energy/light is emitted

๏ Calculate ionization energy
Ionization of Hydrogen
๏ Calculate ionisation energy
๏ Explain the line spectrum of hydrogen according
to Planck equation

๏ If,

๏ Then,
Inadequacies of Bohr Model
๏ 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
๏ 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
 Wave-Particle Duality
๏ 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 wave-
particle duality with the equation:
 Every object in momentum (p) will possess a wavelength (λ)

Mass velocity λ
Particle
(kg) (m s-1) (10-12 m)

Electron (gas) 9 x 10-31 1 x 105 7000

He atom (gas) 7 x 10-27 1000 90

Base ball 0.1 20 3 x 10-22

๏ 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 ELECTRON DIFFRACTION

[WAVE] [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:

๏Uncertainty in momentum is:

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.