BITS Pilani

Pilani Campus

CHEM F111 General Chemistry

Lecture 6
QUANTUM THEORY- ORIGINS
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 Quantum Theory (Lecture 6-9)
-Experimental Observations: Failures of Classical Mechanics
Blackbody Radiation; Heat Capacity of Monoatomic solids; Atomic and
Molecular Spectra; Bohr’s Model of Hydrogen-like atom; Photoelectric
Effect
-Quantization
-Particle Character of Light
-de Broglie Matter Waves
-Wave-Particle Duality
-Heisenberg Uncertainty Principle
-Quantum Mechanics-Introduction: Wavefunction; Observables and
Operators; Born Interpretation of Wavefunction: Probability; Normalization
The Schrodinger Equation: Solutions for: Translation; Rotation and
Vibration 2
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 What is a Physical Law?
Statement of nature which each experimenter must arrive at -
Describes the physical world

Laws formulated with observations: depends on accuracy of

instruments
Advancement of technology leads to better instrumentation

Laws that remain true gain in stature, those which don’t must be
abandoned
Classical Mechanics: (Galileo, Newton, Euler, Lagrange Hamilton)
unaltered for three centuries
Some History…
Beginning of last century two entities---Matter & Radiation
Matter described by Newton’s laws
Radiation by Maxwell’s equation
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 Classical Mechanics: A Brief Review

Direct Consequences:
1. Predict a precise trajectory for particles with precisely
specified locations and momenta at each instant.

2. Allows the translational, rotational and vibrational modes of

motion to be excited to any energy simply by controlling the
forces that are applied.

3. Classical Mechanics: Waves and Particles are distinct concepts

It was thought that we now understood all…

First breakthrough came with radiations emitted by a black body

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 Quantum Theory - Origins
Thermal-Radiation
Observations:
When a material is heated, it radiates heat and its color depends on
its temperature
Example: heating elements of a stove:
– Dark red: 550ºC – Bright red: 700ºC – Then: orange, yellow and
finally white (really hot !)

The emission spectrum depends on the material

Theoretical description:- simplifications necessary
Blackbody!!
Black-Body Radiation
Blackbody radiation concerns about the energy (power) profile of the
radiation wave emitted from a blackbody at given temperature (i.e. in
thermal equilibrium with radiation)
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 Why Blackbody

A blackbody is a perfect absorber:– Incoming

radiations is totally absorbed and none is
reflected
Expt.: Pinhole in an empty container maintained
at constant temperature
– Incoming radiations entering the hole keep
bouncing around inside the box with negligible
chance of escaping again through the hole
Absorbed.

The hole is the perfect emitter, the blackbody Radiation emitted

does not depend on the material the box is made of
=> Universal in nature

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 Blackbody Radiation
-The radiation is reflected many times in the
container and comes to thermal equilibrium
with the walls at a temp. T
-The Radiation leaking out through the
pinhole is the blackbody radiation at temp. T

Study the distribution of the radiant energy (Power) over different

wavelengths, at constant temperature

Emissive Power, J (λ, T) = Energy radiated per unit area per second in
the range λ and λ + dλ
Wavelength difference dλ

Energy density E(λ,T) is proportional to J(λ,T)

Energy per unit volume associated with energy of radiation of wavelength λ to λ+dλ

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 Spectrum of a Blackbody
Some Observations (Experimental
Result):

1. J (λ, T) increases with increase in T

2. At const. T, J (λ, T) increases as λ
increases, attains a maximum value
and then decreases.
3. With increase in T, the λmax shifts
towards shorter wavelength.
λmax T = constant (2.9mmK)
[Wien’s Displacement Law]
4. Area under the curve at any T =
Total Emissive Power : Increases
rapidly with increase T;
M=∫(J (λ, T) dλ = σT4
[Stefan-Boltzmann Law]
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 Understanding Blackbody Radiation Spectrum
Classical Physics: Rayleigh-Jeans Law
Assumptions:
-Electromagnetic Field as a collection of oscillators of all possible
frequencies
-Presence of radiation of frequency ν signifies that electromagnetic
field of that frequency is excited

Principle of equipartition of energy was applied to calculate the

average energy of the oscillator

Rayleigh-Jeans Law:
Energy Density dE (Amount of energy per unit volume in the
wavelength range of λ to λ+dλ is Two factors in dE: (i) no. of oscillators per
unit volume with wavelength in the given
dE = ρdλ; ρ = (8π/ λ4 )kT; range
= (8π/ λ4 ) dλ kT (ii) Average energy at equilibrium of an
oscillator
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Limitations in Rayleigh-Jeans Law
Quite Successful at long wavelengths
Short wavelengths-
As λ decreases, ρ = (8π/ λ4 )kT
increases without going through
maxima
-Predicts that oscillator of very short
wavelengths are strongly excited even at
room temp.
-Large amount of energy is radiated in
the high frequency region of the
electromagnetic spectrum
-Cool objects should also radiate in the
visible & UV region!!!
Infinite energy density at short wavelengths. UV Catastrophe!!
Thermal Motion of the atoms in the walls of the blackbody excites the oscillators the
EMR. According to classical mechanics, all the oscillators of the field share equally
in the energy supplied by the walls. So even the higher frequency oscillators are
excited!!!
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 Wien’s Radiation Law

Later on in 1896, Wien derived another important formula using

thermodynamics
ρ(λ,T)dλ = α λ-5e-βc/λTdλ
Assumptions:

1. The radiation inside a hollow enclosure is produced by

resonators of molecular dimensions
2. The frequency of the radiation emitted is proportional to the
kinetic energy of the resonators
3. The intensity of radiation of any particular wavelength is
proportional to the number of resonators having the required
amount of energy
Limitations: Explains the experimental results fairly well for low values of
λT but for higher values of it gives values of Energy Density lower than
the experimental value
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Planck’s Explanation

Assumptions:

-Energy of each electromagnetic oscillator is limited to discrete

values and cannot be varied arbitrarily
[Contrary to the view point of classical physics – on which the
equipartition principle used by Rayleigh is based]

-Oscillators can absorb or emit energy in discrete multiples of

fundamental quantum of energy given by ΔE=hν

Limitation of energies to discrete values is called the

quantization of energy

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Planck’s Explanation: Quantization
Quantization Hypothesis: Permitted energies of an electromagnetic
oscillator of frequency ν are integral multiple of hν.
E = nhν; n= 0,1,2,3…..

As long as the oscillator has energy equal to one of the allowed

values, it cannot emit or absorb energy. [Stationary state or a quantum
state of energy]

Emission or absorption of energy

occurs only when the oscillator
jumps from one energy state to
another.

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Planck Radiation Law
dE = (8π/λ4) dλ (hc/λ) {exp(hc/λkT) -1}-1
The density of the oscillators are the same, but the average energy is different from
that in classical physics. k= Boltzmann Constant
The value of h, which was an undetermined parameter in the theory was obtained by
varying until a best fit was obtained. [h = 6.626×10-34 Js; Planck’s Constant]

Consequences of Planck’s Law:

1. For short wavelengths, when hc/λ >> kT;
Energy of oscillator approaches to zero
[Wein’s Radiation Law]
2. For long wavelengths,
when hc/λ << kT;
Energy of oscillator = kT
[Reduces to Rayleigh-Jeans law]
3. Wein’s Displacement Law

4. Stefan-Boltzmann Law

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