Atomic Structure

Within the late nineteenth century most of the scientists accepted the following basic
properties of atoms:

1. Atoms are very small, about 0.1 nm (0.1 × 10−9 m) in radius.

2. Atoms are stable—they do not spontaneously break or collapse; therefore the internal
forces that hold the atom together must be in equilibrium.

3. Atoms contain negatively charged electrons (discovered by J.J. Thomson in 1897),

but are electrically neutral, so positively charged matter of some kind must be present.
If we disturb an atom or collection of atoms with sufficient force, electrons are
emitted (photoelectric effect discovered in 1887 by the German physicist Heinrich
Rudolf Hertz).

4. Atoms emit and absorb electromagnetic radiation. (The first spectral series of
hydrogen atom was discovered by J.J. Balmer in 1885).

 But what type of charges and how are they arrange?

 Sir Joseph John Thomson (1856-1940)

 Born in Manchester, England.

 Achieved Bachelor in mathematics from Trinity

College, Cambridge.

 Became Professor of Physics at the University of

Cambridge.

 Credited with the discovery of the electron (the

first subatomic particle).

 awarded the Nobel Prize in Physics in 1906 for his

work on the conduction of electricity in gases.

 Was the 42nd President of the Royal Society.

 Thomson’s atom model
In 1898 British physicist J. J. Thomson proposed that

 Atoms are just positively charged lumps of

matter which is spherical in shape. The whole
mass of the atom is evenly distributed and the
positive charges are distributed all over the
mass within which electrons are embedded,
like raisins in the fruit cake.

 The whole positive charge of the atom is equal to the total charge of electrons.

 The electrons oscillate or vibrate about their mean position.

 This is also known as plum pudding or sometimes water melon model.

 Since Thomson had played an important role in the discovery of electron,
his idea about atom was taken seriously by the scientists.
Success:

 This model explained the emission of electrons in thermionic process (by

heating) and in photoelectric effect.

 It provided a mechanism for the emission of electromagnetic waves. The

electromagnetic waves were supposed to be emitted by oscillating bound
electrons in the atoms.

Limitation:

The model could not explain the phenomenon of atomic spectra, which is the
emission and absorption of specific wavelengths of light by atoms.
Earnest Rutherford (1871-1937)

 Born in New Zealand.

 Studied (postgraduate) at Cambridge University under the

mentorship of J.J. Thomson.

 In 1907 became professor of Physics at Manchester,

England.
 In 1919 became the director of Cavendish laboratory,
Cambridge.

 Known for his pioneering work on alpha-particle scattering

and radioactive decays and described as "the father of
nuclear physics”.

 Awarded the Nobel Prize in Chemistry for his

investigations into the disintegration of the elements, and
the chemistry of radioactive substances in 1908.
Alpha particle scattering experiment

At the suggestion of Ernest Rutherford, Hans Geiger and Ernest Marsden

performed it in 1911. Alpha particles are helium atoms that have lost of two
electrons each, leaving them with a charge of +2e.

They placed a fast alpha particle emitting radioactive substance behind a lead
collimator so that a narrow beam of alpha particles was produced. The beam was
directed at a thin gold foil. A zinc sulfide screen, which gives off a visible flash
of light when struck by an alpha particle, was set on the other side of the foil
with a microscope to see the flashes.

The Rutherford alpha-particle

scattering experiment
 It was expected that the alpha particles would go right through the foil with
hardly any deflection according to Thomson model. With only weak electric
forces exerted on them, alpha particles that pass through a thin foil ought to be
deflected only slightly, 1 degree or less.

What they actually observed?

They found that most of the alpha particles indeed were not deviated by much, a
few were scattered through very large angles. Some were even scattered in the
backward direction. As Rutherford remarked, “It was as incredible as if you fired
a 15-inch shell at a piece of tissue paper and it come back and hit you.”

Alpha particles are relatively heavy (~8000 electron masses) with high speeds
(2×107 m/s) used in this experiment. So it was clear that powerful forces were
needed to cause such marked deflections.
 With an atom being largely an empty space as most of the alpha particles go
right through the thin foil. However, when an alpha particle happens to come
near a nucleus, the intense electric field scatters it through a large angle. The
atomic electrons, being so light, do not appreciably affect the alpha particles.
The results of such scattering experiments led Rutherford to propose that the
mass and positive charge of the atom are not distributed uniformly over the
volume of the atom, instead, are concentrated in an extremely small region.

Rutherford atom model

From the results of alpha particle scattering experiment

Rutherford proposed his atom model:

 An atom is being composed of a tiny nucleus in

which its positive charge and nearly all its mass are
concentrated, with the electrons some distance away
revolving round the nucleus. The dimensions of the
nucleus and of the electrons are negligibly small as
compared to the overall size of the atom, so that Rutherford model of
most of the volume occupied by an atom is actually the atom
an empty space.
 The electrons could not be stationary because there is nothing that can keep
them in place against the electric force pulling them to the nucleus. The
electrons must be revolving around the nucleus in closed orbits, so that the
centrifugal force due to the rotation of the electron is balanced by the force of
electrostatic attraction between the nucleus and the electrons. Thus a dynamic
planetary model is possible in which nucleus plays the role of the sun and
electrons correspond to the individual planets of the solar system.

Electron orbits

Let us look at the classical dynamics of the

hydrogen atom, whose single electron makes it the
simplest of all atoms. We assume a circular orbit
instead of elliptical for convenience. The
centripetal force is

𝑚𝑣 2
𝐹𝑐 =
𝑟
Force balance in
hydrogen atom
The total energy of the electron is negative. This holds for every atomic electron
and reflects the fact that it is bound to the nucleus. If E were greater than zero,
an electron would not follow a closed orbit around the nucleus.

Actually, of course, the energy E is not a property of the electron alone but is a
property of the system of electron + nucleus.
Failure of Rutherford atom model
 According to electromagnetic theory, accelerated electric charges radiate
energy in the form of electromagnetic waves. An electron pursuing a curved
path is accelerated and therefore should continuously lose energy, spiraling
into the nucleus in a fraction of second. But the atoms are stable, do not
collapse.

Fig.: An atomic electron should classically

spiral rapidly into the nucleus as it reduces
energy due to its acceleration.

 Atomic stability is not the only thing but also the existence of characteristic
spectral lines can not be explained by Rutherford model.
The failure of Classical Physics
Newton’s laws of motion and Coulomb’s law of electric force- both are the pillars of
classical physics- have been used for the analysis of stability of atom in Rutherford atom
model. However, it is not in accord with electromagnetic theory-another pillar of classical
physics.

Atomic stability is not the only thing but also the existence of characteristic spectral lines
is another important aspect of the atom that finds no explanation in classical physics.

Actually, the laws of physics that are valid in the macroworld do not always hold true in
the microworld of the atom.

Classical physics fails to provide meaningful analysis of atomic structure because it

approaches nature in terms of pure particles and pure waves. In reality particles and
waves have many properties in common, though the smallness of Planck’s constant
makes the wave-particle duality imperceptible in the macroworld. The usefulness of
classical physics decreases as the scale of the phenomena decreases, and we must allow
for the particle behavior of waves and wave behavior particles to understand the atom.
Atomic spectra

When an atomic gas or vapor at somewhat less than atmospheric pressure is suitably
excited usually by passing an electric current through it, the emitted radiation has a
spectrum which contains certain specific wavelengths only. An idealized arrangement
for observing such atomic spectra is shown in the following Fig. however, actual
spectrometers use diffraction grating.

Fig.: An idealized spectrometer.

Fig. shows the emission line spectra of several elements. Every element displays a
unique line spectrum when the sample of it in the vapor phase is excited.
Spectroscopy is therefore a useful tool for analyzing the composition of an unknown
substance.
 Fig.: Some of the principal lines in the
emission spectra of hydrogen, helium and
mercury.

When white light is passed through a gas, the gas is found to absorb light of certain
wavelengths present in its emission spectrum. The resulting absorption line spectrum
consists of a bright background crossed by dark lines that correspond to the missing
wavelengths; emission spectra consist of bright lines on a dark background.

Fig.: The dark lines in the absorption spectrum of an element

correspond to bright lines in its emission spectrum.
 Bohr Atom Model
Bohr assumed basically Rutherford nuclear-model of the atom and tried to overcome the
defects of the model. He proposed the following two postulates.

Basic Postulates:
(1) An electron cannot revolve round the nucleus in all possible orbits as suggested by
the classical theory. The electron can revolve round the nucleus only in those allowed
or permissible orbits for which the angular momentum of the electron is an integral
multiple of h/2π. Here, h is the Planck’s constant = 6.64 × 10–34 Js. These orbits are
called stationary orbits and an electron revolving in these orbits does not radiate
energy.

Explanation: For an electron of mass m, moving with a speed v in an orbit of radius r, L

= mvr = mr2ω = nh/2π. n is called the Principal quantum number. It takes integral values,
excluding zero; n = 1, 2, 3, 4 .......

(2) An atom radiates energy only when an electron jumps from a stationary orbit of
higher energy to one of lower energy. If the electron jumps from an initial orbit of energy
Ei to a final orbit of energy Ef (Ei > Ef ), a photon of frequency, ν = (Ei - Ef)/h is emitted.
Bohr’s postulates are the combination of some of the ideas of classical physics and
quantum physics. Here the energy levels are quantized. It means that the electrons
can move only in some particular orbits of definite radii and not all radii as
suggested by Rutherford’s model.

Based on these postulates, Bohr derived the formulae for (i) the radii of the
stationary orbits and (ii) the total energy of the electron in the orbit.

Consider an atom whose nucleus has a positive charge Ze and mass M. For
hydrogen, Z = 1. Let an electron of charge (–e) and mass m move round the nucleus
in an orbit of radius r. Since M >> m, the nucleus is stationary.
The energies specified by equation (8)
are called the energy levels of the
hydrogen atom and are plotted in the
Figure. These levels all are negative,
which signifies that the electron does
not have enough energy to escape from
the nucleus. An atomic electron can
have only these energies and no others.

The lowest energy level 𝐸1 is called the

ground state of the atom, and the higher
levels 𝐸2 , 𝐸3 , 𝐸4 ,……are called excited
states.

Fig.: Energy levels of the hydrogen atom.

As the quantum number n increases, the corresponding energy 𝐸𝑛 approaches
closer to zero. In the limit of 𝐸 = ∞, and 𝐸𝑛 = 0 and the electron is no longer
bound to the nucleus to form an atom.

A positive energy for a nucleus-electron combination means that the electron is

free and such a combination does not constitute an atom.

The work needed to remove an electron from an atom in its ground state is called
its ionization energy. The ionization energy is accordingly equal to −𝐸1 , the
energy that must be provided to raise an electron from its ground state to an
energy of 𝐸 = 0, when it is free. In the case of hydrogen, the ionization energy is
13.6 eV since the ground-state energy of the hydrogen atom is -13.6 eV.
Bohr’s interpretation of the hydrogen spectrum
Spectral series of hydrogen atom
Brackett and Pfund series lie in the very far infrared
region of the hydrogen spectrum. By putting 𝑛 = ∞
in each one of the series, we get the wavenumber of
the series limit, i.e., the last line of the series. The
electron jumps giving rise to the different series in
hydrogen are shown in the Figure.

 Energy-level diagram
The equation
−𝑚𝑒 4 𝑍 2
𝐸𝑛 =
8𝜀0 2 𝑛2 ℎ2

Can be diagrammatically represented. Then, it is called the energy-level diagram.

 Substituting the values of 𝑚, 𝑒, 𝜀0 and ℎ we get for hydrogen (Z=1)

In the energy-level diagram,

the discrete energy states are
represented by horizontal
lines and the electronic
jumps between these states
by vertical lines. Fig. shows
schematically how spectral
lines are related to atomic
energy levels.

Fig.: Energy-level diagram

 De Broglie Model of the Atom
The experiments on interference, diffraction and polarization established the wave
nature of light. The experiments on photo-electric effect established the corpuscular
nature of light. Einstein’s equation, 𝐸 = 𝑚𝑐 2 gives relation of conversion of mass into
energy. De Broglie noticed that the corpuscular nature of light is more obvious for more
energetic light i.e., light of shorter wavelength. Thus the light particle known as a
photon has corpuscular as well as wave nature. This dual behavior of photons inspired
De Broglie to suggest a model of the atom.

De Broglie suggested that particles like electrons have also a wave nature similar like
photons.

For a particle Einstein’s equation is

2
𝑚 0 𝑐
𝐸 = 𝑚𝑐 2 = … … … … … … … … … … … … … … … (1)
𝑣 2
1− 2
𝑐

Here 𝑚0 is the rest mass. The energy of a wave of frequency 𝜈 according to Planck is
𝐸 = ℎ𝜈 … … … … … … … … … … … … … … … … … … … … (2)
From (1) and (2),
2
𝑚0 𝑐 2
hν = 𝑚𝑐 =
𝑣2
1− 2
𝑐
But, 𝜈𝜆 = 𝑐
ℎ𝑐
∴ = 𝑚𝑐 2
𝜆
ℎ
⟹ 𝜆=
𝑚𝑐

For an electron of velocity 𝑣

𝑣2
ℎ ℎ 1− 2
𝑐
𝜆= =
𝑚𝑣 𝑚0 𝑣

For electrons, the wavelength is longest, while for protons it is smaller than the
electrons. If the value of h, m and v are substituted, 𝜆 is found to be very small.
Thus, the De Broglie model of an atom has electrons in various orbits and the electrons
behave as matter waves of wavelength
ℎ
𝜆= .
𝑚𝑣

The electron exists as a standing wave in each orbit. The energy levels and “orbits” of
the Bohr model are retained. Moreover, this model explains the Bohr’s postulates.

The electrons can be only in those orbits whose circumference can contain the complete
wave of the electron or the length of the orbit is a whole number multiple of the
wavelength.

The electron can not be in an orbit whose length is not a whole number multiple of the
wavelength.
So, the condition for orbit stability,

2𝜋𝑟𝑛 = 𝑛𝜆 𝑛 = 1, 2, 3, … … … … … .

Where 𝑟𝑛 designates the radius of orbit with n wavelengths and the integer n is the
quantum number of the orbit.

But,
ℎ
𝜆=
𝑚𝑣

𝑛ℎ
⟹ 2𝜋𝑟𝑛 =
𝑚𝑣

𝑛ℎ
∴ 𝑚𝑣𝑟𝑛 = … … … … … … … … … … . (3)
2𝜋

Equation (3) is in agreement with the Bohr’s quantization hypothesis. Thus the
electrons are matter waves in various orbits round the nucleus.
Bohr atom model (different approach)

The first theory of atom to meet any success was put forward in 1913 by Niels Bohr. The
concept of matter waves leads in a natural way to this theory, as de Broglie found.
Bohr himself used a different approach, since de Broglie’s work came a decade later,
which makes his achievement the more remarkable. The results are exactly same, however.

We consider the wave behavior of an electron in orbit around a hydrogen nucleus. The de
Broglie wavelength of this electron is
𝑣2
ℎ ℎ 1− 2
𝑐
𝜆= =
𝑚𝑣 𝑚0 𝑣
𝑣2
Since the electron velocities are much smaller than c, we can consider 1 − = 1,
𝑐2
and the electron velocity can be written as
𝑒
𝑣=
4𝜋𝜖0 𝑚𝑟
ℎ 4𝜋𝜖0 𝑟
Hence electron wavelength 𝜆= … … … … … … … … . (1)
𝑒 𝑚
By substituting 5.3×10-11 m for the radius r of the electron orbit we can find the
electron wavelength:

The orbit of the electron in a hydrogen

atom corresponds to one complete electron
wave joined on itself as shown in the
Figure.

Fig.: The orbit of the electron in a hydrogen atom

This can be explained by considering the vibrations of a wire loop as shown in the
Figure, we find that their wavelengths always fit an integral number of times into
the loops circumference so that each wave joins smoothly with the next. If the
wire were perfectly elastic, these vibrations would continue indefinitely.

Fig.: Some modes of vibrations of a wire loop. In each case a whole number of wavelengths fit into
the circumference of the loop.
Why are these only vibrations possible in a wire loop?

If a fractional number of wavelengths is placed around the loop as shown in the Fig.,
destructive interference will occur as the waves travel around the loop and the
vibrations will die out rapidly.

Fig.: A fractional number of wavelengths can not persist because

destructive interference will occur.

By considering the behavior of electron waves in the hydrogen atom as analogous to

the vibrations of a wire loop, we can say that

An electron can circle a nucleus only if its orbit contains an integral number of de
Broglie wavelengths.
This statement combines both the particle and wave characters of the electron since
the electron wavelength depends upon the orbital velocity needed to balance the
pull of the nucleus. To be sure, the analogy between an atomic electron and the
standing waves represents an illuminating step along the path to the more profound
and comprehensive, but also more abstract, quantum-mechanical theory of the
atom.

The circumference of a circular orbit of radius r is 2πr, and so the condition for
orbit stability is

𝑛𝜆 = 2𝜋𝑟𝑛 𝑛 = 1, 2, 3, … … … … . .

Where 𝑟𝑛 designates the radius of the orbit that contain n wavelengths. The integer
n is called the quantum number of the orbit.
Substituting for electron wavelength, λ we can obtain