PLANCK’S THEORY

Electromagnetic radiation refers to waves of the electromagnetic spectrum propagating through space
carrying electromagnetic radiant energy. It includes radio waves, microwaves, infrared, visible light
(ROYGBIV), UV, X-rays and gamma rays.

The classical wave theory of light by Maxwell explains that light is an electromagnetic radiation
(wave) that travels at the speed of 3 x 108 m/s. The equation c = f λ explains that the speed of light is
directly proportional to its frequency and wavelength.

The classical wave theory was only able to explain phenomena such as reflection, refraction,
diffraction, interference and polarization. It failed to explain phenomena such as blackbody radiation,
photoelectric effect and energy quantization which Plank’s quantum theory of light explains.

Black body radiation:

All objects emit electromagnetic radiation when they have temperatures above absolute zero (-273 0C or
0 K) and conversely, they also absorb electromagnetic radiation to some degree. An object that absorbs
all radiation falling on it at all wavelengths is called a blackbody. When a black body is at uniform
temperature, its emission has a characteristic frequency distribution that depends on the temperature.
This emission is called blackbody radiation.

Blackbody radiation curve

The experimental behaviour of blackbodies differ from the classical Physics theory of Rayleigh
and Jeans because the blackbody emission spectrum shows that the intensity increases with increasing
frequency and temperature till it reaches the UV region where it peaks and begins to decrease. This sharp
deviation at the UV region was then referred to as the UV catastrophe. Since the classical theory couldn’t
explain this, quantum theory of light came into being. This is what led to Planck’s theory in 1900.

Planck theorized that electromagnetic radiation can be emitted or absorbed only in discrete
packets called quanta of energy (not continuous like classical theory explains).

Equanta = hf = hc/ λ

Where h = Planck’s constant, f = frequency of radiation, λ = wavelength and c = speed of light.

This assumption or formula aligned with the blackbody radiation curve.

In 1905, Albert Einstein solved the problem by postulating that the quanta or packets of light were
real physical particles which are called photons. This was achieved by studying the photoelectric effect.

Photoelectric Effect:

The photoelectric effect is the emission of electrons when electromagnetic radiation such as light
is incident on a material. The results of the photoelectric effect differ from classical electromagnetism
which predicts that continuous light waves transfer energy to electrons which would then be emitted
when they accumulate enough energy i.e., as intensity increases, the energy of emitted electrons should
also increase, but this wasn’t the case with the photoelectric effect because because no electrons were
emitted until light of a particular frequency was radiated.

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 Thus, emission and kinetic energy of electrons are dependent on the frequency of radiation and
not the intensity. Thus, a dim light of high frequency will eject electrons, while a bright light of low
frequency will not eject electrons. This explains the UV catastrophe where there was decline in intensity
despite increasing frequency.

Photoelectric effect

BOHR’S THEORY

Atomic emission spectra:

Electrons in an atom arranged such that the energy of the atom is as low as possible. So the ground
state of an atom is the lowest state of the atom. When those atoms are given energy, the electrons move
to a higher energy level. These energy levels of the electrons in atoms are quantized, that is they are
discrete, such that an electron moves from energy level 1 to 2 to 3 e.t.c. An electron canot move from
energy level 1 to 1.5. an excited state of an atom is a state where its potential energy is higher than the
ground state. An atom in the excited state is not stable, so it returns to its ground state releasing the
energy it had previously gained in the form of electromagnetic radiation.

Atoms gain energy when electric current passes through an enclosed sample of its gas at low
pressure. So every gas discharge tube glows with a distinctive colour depending on the identity of the gas.
For example, during the flame test, sodium gives off a brilliant yellow light. When this light was examined
using a spectroscope, it was found that it doesn’t consist of a continuous range of colours like that of a
rainbow or the spectrum obtained from white light. Instead, the light emitted is composed of discrete
lines of different colours. This kind of spectrum is known as line emission spectrum.

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 Atomic/ Line Emission Spectra

Niels Bohr investigated the light obtained from a hydrogen discharge tube and found it to be made
of lines. Similarly, all atoms have distinctive line spectra when they are caused to emit light. The
wavelengths of the lines are characteristic of the element. So the line spectra generated by an element is
like a fingerprint that is specific for that element. That is, hydrogen will not have same line spectra as
chlorine or lithium.

The atomic spectra of hydrogen can be divided into five series of lines, each characterized bya
particular energy, n, level. Balmer in 1985 found that wavelengths of the lines in the visible spectrum of
hydrogen could be calculated by a particular formula. Further work showed that this formula is applicable
to other series of lines from other atoms. This was made to fit into an equation known as Rydberg’s
equation.

Where λ = wavelength, R = Rydberg’s constant, nf / n1 = final energy level, ni / n2 = initial energy

Calculations……

1. The yellow light given off by sodium lamp has a wavelength of 589 nm. What is the frequency of
this radiation?

2. Calculate the energy of one photon of yellow light that has a wavelength of 589 nm.

3. Calculate the wavelength of light emitted when a hydrogen atom relaxes from n = 6 to n = 2.

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The complete atomic spectrum of hydrogen can be divided into five series of lines, each characterized by
one particular n value

Hydrogen Atomic Spectrum

Bohr’s Postulates of the hydrogen atom:

The discovery of the hydrogen atom line spectra led Neils Bohr to give the following postulates:

1. In an atom, electron revolve around the positively charged nucleus in a definite circular path
called orbits or shells

2. Each orbit or shell has a fixed energy

3. The energy levels are represented by an integer (n=1, 2, 3) known as principal quantum number.

4. When an electron absorb energy, it moves to a higher energy level and same electron returns to
its initial lower energy level emitting radiation in the process.

5. The energy of radiation absorbed or emitted is equal to the difference in energy levels the
electron transited

WAVE THEORY OF THE ATOM

Electrons revolve around circular orbits in discrete energy levels according to Neils Bohr. Since
there is an electrostatic force of attraction between the positively charged protons and electrons,
electrons should actually crash into the nucleus, but this doesn’t happen in reality. Bohr’s reasoning was
similar to why planets that revolve around the sun are not drawn into the sun. This was based on the
proposal that the centrifugal force of the revolving electron just exactly balances the attractive force of

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the nucleus (in analogy with the centrifugal force of the moon in its orbit exactly counteracting the pull of
the earth’s gravity). This hypothesis seemed acceptable because of the interactions between gravity and
coulomb’s interactions. According to Newton’s law of gravity, the force of gravity between two masses is
expressed as

Also, the expression for the Coulomb force between two charged species is

However, an electron is electrically charged (unlike a planet or satellite) and it has been known
since the mid-19th century that an electric charge that undergoes acceleration (changes in velocity and
direction) will emit electromagnetic radiation, losing energy in the process. According to classical
mechanics, the electron would simply spiral into the nucleus and the atom would collapse.

In 1924, de Broglie came up with the wave theory of an atom which assumes that electrons show
wavelike properties. The wavelike properties of the electron make it very elusive (difficult to find or catch).
This led Heisenberg in 1927 to postulate his famous uncertainty principle. According to this principle, if
we measure the momentum of an electron accurately, we cannot know its position and vice – versa. Based

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on Bohr’s theory, electrons revolve around the nucleus in circular orbits or shells which are known as the
principal quantum number designated by ‘n’.

The wave mechanics model doesn’t restrict electrons to certain energy levels only. Instead, it
describes a region around the nucleus called orbital where there is a possibility of finding an electron with
a certain amount of energy. This was derived from the wave function from Schrodinger’s equation.

Wave nature of the atom

So according to the wave mechanics model, the orbital is identified by a set of quantum numbers.
Therefore, to predict how electrons are arranged in space, we have to examine the energy levels in an
atom. The ability of an electron to both function as a particle and as a wave is known as wave-particle
duality.

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Degeneracy of Atomic Orbitals:
Degeneracy of atomic orbitals is the existence of orbitals having the same energy. An atom has
four orbitals, namely s, p, d, and f. The p orbital has three orbitals px, py, and pz. All these three
orbitals have similar energy belonging to the same orbital (p), hence are called degenerate
molecular orbitals.
Shapes of Atomic Orbitals:

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ELECTRONIC CONFIGURATION

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