Structure of Atoms

DEVELOPMENTS LEADING TO THE BOHR’S MODEL OF ATOM

Two developments played a major role in the formulation of Bohr’s model of atom. These
were:
(i) Dual character of the electromagnetic radiation which means that radiations
possess both wave like and particle like properties, and
(ii) Experimental results regarding atomic spectra.
Wave Nature of Electromagnetic Radiation:
When electrically charged particle moves under acceleration, alternating electrical and
magnetic fields are produced and transmitted. These fields are transmitted in the forms of
waves called electromagnetic waves or electromagnetic radiation.
Properties of electromagnetic radiations:
1. The oscillating electric and magnetic fields produced by oscillating charged particles
are perpendicular to each other and both are perpendicular to the direction of
propagation of the wave.
2. Electromagnetic waves do not require medium and can move in vacuum.
3. There are many types of electromagnetic radiations, which differ from one another in
wavelength (or frequency). These constitute what is called electromagnetic spectrum.

The characteristic properties of waves are:

i) Frequency (ν). The SI unit for frequency (ν) is hertz (Hz, s–1). It is defined as
the number of waves that pass a given point in one second.
ii) wavelength (λ). The SI unit for wavelength is meter (m).
In vacuum all types of electromagnetic radiations, regardless of wavelength, travel at the
same speed, i.e., 3.0 × 108 m s–1. This is called speed of light and is given the symbol ‘c’.
The frequency (ν), wavelength (λ) and velocity of light (c) are related by the equation
c=νλ
Radiation could be sub-divided into discrete chunks of energy. Atoms and molecules could
emit or absorb energy only in discrete quantities of energy named as quantum. Quantum is
the smallest quantity of energy that can be emitted or absorbed in the form of
electromagnetic radiation. The energy (E) of a quantum of radiation is proportional to its
frequency (ν) and is expressed by equation
E=hυ
The proportionality constant, ‘h’ is known as Planck’s constant (6.626×10–34 J s).
Light possesses both particle and wave-like properties, i.e., light has dual behaviour.
Depending on the experiment, we find that light behaves either as a wave or as a stream of
particles. Whenever radiation interacts with matter, it displays particle like properties in
contrast to the wavelike properties which it exhibits when it propagates.

An absorption spectrum:
It is like the photographic negative of an emission spectrum. A continuum of radiation is
passed through a sample which absorbs radiation of certain wavelengths. The missing
wavelength which corresponds to the radiation absorbed by the matter, leave dark spaces in
the bright continuous spectrum.

Emission spectrum:
To produce an emission spectrum, energy is supplied to a sample by heating it or irradiating
it with radiation. Atoms, molecules or ions that have absorbed radiation are said to be
“excited”. The spectrum of radiation emitted by a substance that has absorbed energy is
called an emission spectrum.

The study of emission or absorption spectra is referred to as spectroscopy. Each element has
a unique line emission spectrum. The characteristic lines in atomic spectra can be used in
chemical analysis to identify unknown atoms in the same way as fingerprints are used to
identify people.
BOHR’S MODEL FOR HYDROGEN ATOM
1. The electron in the hydrogen atom can move around the nucleus in a circular path of
fixed radius and energy. These paths are called orbits. These orbits are arranged
concentrically around the nucleus.
2. The energy of an electron in the orbit does not change with time. However, the
electron will move from a lower stationary state to a higher stationary state when
required amount of energy is absorbed by the electron or energy is emitted when
electron moves from higher stationary state to lower stationary state. The energy
change does not take place in a continuous manner.
3. The frequency of radiation absorbed or emitted when transition occurs between two
stationary states that differ in energy by ∆E.
∆ E = h υ (∆E = E1-E2)
E1 and E2 are the energies of the lower and higher allowed energy states, respectively.
This expression is commonly known as Bohr’s frequency rule.
4. The angular momentum of an electron is quantised. In a given stationary state it can
be expressed as
𝑛ℎ
mevr =
2𝜋

where, n = 1,2,3……, me is the mass of electron, v is the velocity and r

is the radius of the orbit in which electron is moving.
Thus, an electron can move only in those orbits for which its angular momentum is integral
multiple of h/2π. That means angular momentum is quantised. Radiation is emitted or
absorbed only when transition of electron takes place from one quantised value of angular
momentum to another.
TOWARDS QUANTUM MECHANICAL MODEL OF THE ATOM
Two important developments which contributed significantly in the formulation of quantum
mechanical model of the atom were:
1. Dual behaviour of matter,
2. Heisenberg uncertainty principle.
Dual Behaviour of Matter:
The French physicist, de Broglie, proposed that matter, like radiation, should also exhibit
dual behaviour i.e., both particle and wavelike properties. This means that electrons should
also have momentum as well as wavelength. de Broglie, from this analogy, gave the
following relation between wavelength (λ) and momentum (p) of a material particle.
ℎ ℎ
λ= =
𝑚𝑣 𝑝

where m is the mass of the particle, v its velocity and p its momentum.
Heisenberg’s Uncertainty Principle:
Heisenberg stated uncertainty principle which is the consequence of dual behaviour of
matter and radiation. It states that it is impossible to determine simultaneously, the
exact position and exact momentum (or velocity) of an electron.
ℎ
Δx.Δp =
4𝜋
ℎ
Δx.mΔv =
4𝜋
ℎ
Δx.Δv =
4𝜋𝑚
where ∆x is the uncertainty in position and ∆p (or ∆v) is the uncertainty in momentum (or
velocity) of the particle. If the position of the electron is known with high degree of
accuracy (∆x is small), then the velocity of the electron will be uncertain [∆(v) is large]. On
the other hand, if the velocity of the electron is known precisely (∆(v) is small), then the
position of the electron will be uncertain (∆x will be large).
Significance of Uncertainty Principle:
Heisenberg Uncertainty Principle rules out existence of definite paths or trajectories of
electrons and other similar particles.
(The effect of Heisenberg Uncertainty Principle is significant only for motion of
microscopic objects and is negligible for that of macroscopic objects.)
Reasons for the Failure of the Bohr Model:
Bohr model of the hydrogen atom, therefore, not only ignores dual behaviour of matter but
also contradicts Heisenberg uncertainty principle.

QUANTUM MECHANICAL MODEL OF ATOM

The branch of science that takes into account the dual behaviour of matter is called quantum
mechanics.
Important Features of the Quantum Mechanical Model of Atom:
1. The energy of electrons in atoms is quantized.
2. Both the exact position and exact velocity of an electron in an atom cannot be
determined simultaneously.
3. An atomic orbital is the wave function ψ for an electron in an atom.
4. The probability of finding an electron at a point within an atom is proportional to the
square of the orbital wave function i.e., | ψ |2 at that point. | ψ |2 is known as
probability density and is always positive.
Orbitals and Quantum Numbers:
1. n defines the shell, determines the size of the orbital and also to a large extent the
energy of the orbital.
2. There are n subshells in the nth shell. l identifies the subshell and determines the
shape of the orbital. There are (2l+1) orbitals of each type in a subshell, that is, one s
orbital (l = 0), three p orbitals (l = 1) and five d orbitals (l = 2) per subshell. To some
extent l also determines the energy of the orbital in a multi-electron atom.
3. ml designates the orientation of the orbital. For a given value of l, ml has (2l+1)
values the same as the number of orbitals per subshell. It means that the number of
orbitals is equal to the number of ways in which they are oriented.
4. ms refers to orientation of the spin of the electron.

Shapes of Atomic Orbitals:

For 1s orbital the probability density is maximum at the nucleus and it decreases sharply
as we move away from it. On the other hand, for 2s orbital the probability density first
decreases sharply to zero and again starts increasing. After reaching a small maximum it
decreases again and approaches zero as the value of r increases further. The region
where this probability density function reduces to zero is called nodal surfaces or
simply nodes. In general, it has been found that ns-orbital has (n – 1) nodes, that is,
number of nodes increases with increase of principal quantum number n. In other words,
number of nodes for 2s orbital is one, two for 3s and so on.
s-orbitals are spherically symmetric, that is, the probability of finding the electron at a
given distance is equal in all the directions. It is also observed that the size of the s
orbital increases with increase in n, that is, 4s > 3s > 2s > 1s and the electron is located
further away from the nucleus as the principal quantum number increases.

p orbital consists of two sections called lobes that are on either side of the plane that
passes through the nucleus. The probability density function is zero on the plane where
the two lobes touch each other. The size, shape and energy of the three orbitals are
identical. They differ however, in the way the lobes are oriented. Since the lobes may be
considered to lie along the x, y or z axis, they are given the designations px, py, and pz.
p orbitals increase in size and energy with increase in the principal quantum number and
hence the order of the energy and size of various p orbitals is 4p > 3p > 2p. The number
of nodes is given by the (n–2), that is number of radial nodes is 1 for 3p orbital, two for
4p orbital and so on.

d-orbitals are designated as dxy, dyz, dxz, dx2–y2 and dz2. The shapes of the first four d-
orbitals are similar to each other, whereas that of the fifth one, dz2, is different from
others, but all five 3d orbitals are equivalent in energy. The d orbitals for which n is
greater than 3 (4d, 5d...) also have shapes similar to 3d orbital but differ in energy and
size.

Besides the radial nodes (i.e., probability density function is zero), the probability
density functions for the np and nd orbitals are zero at the plane (s), passing through the
nucleus (origin). For example, in case of pz orbital, xy-plane is a nodal plane, in case of
dxy orbital, there are two nodal planes passing through the origin and bisecting the xy
plane containing z-axis. These are called angular nodes and number of angular nodes are
given by ‘l’, i.e., one angular node for p orbitals, two angular nodes for ‘d’ orbitals and
so on. The total number of nodes are given by (n–1), i.e., sum of l angular nodes and (n –
l – 1) radial nodes.
Energies of Orbitals
The orbitals having the same energy are called degenerate.
The 1s orbital in a hydrogen atom, as said earlier, corresponds to the most stable
condition and is called the ground state and an electron residing in this orbital is most
strongly held by the nucleus. An electron in the 2s, 2p or higher orbitals in a hydrogen
atom is in excited state.
Within a given principal quantum number, the energy of orbitals increases in the order
s<p<d<f. The main reason for having different energies of the subshells is the mutual
repulsion among the electrons in multielectron atoms. In multielectron atoms, besides the
presence of attraction between the electron and nucleus, there are repulsion terms
between every electron and other electrons present in the atom. Thus, the stability of an
electron in a multi-electron atom is because total attractive interactions are more than the
repulsive interactions.
Due to the presence of electrons in the inner shells, the electron in the outer shell will not
experience the full positive charge of the nucleus (Ze). The effect will be lowered due to
the partial screening of positive charge on the nucleus by the inner shell electrons. This
is known as the shielding of the outer shell electrons from the nucleus by the inner shell
electrons, and the net positive charge experienced by the outer electrons is known as
effective nuclear charge.
Electrons present in spherical shaped; s orbital shields the outer electrons from the
nucleus more effectively as compared to electrons present in p orbital. Similarly,
electrons present in p orbitals shield the outer electrons from the nucleus more than the
electrons present in d orbitals, even though all these orbitals are present in the same
shell.
Further within a shell, due to spherical shape of s orbital, the s orbital electron spends
more time close to the nucleus in comparison to p orbital electron which spends more
time in the vicinity of nucleus in comparison to d orbital electron.
The s orbital electron will be more tightly bound to the nucleus than p orbital electron
which in turn will be better tightly bound than the d orbital electron. The energy of
electrons in s orbital will be lower (more negative) than that of p orbital electron which
will have less energy than that of d orbital electron and so on.
Energies of the orbitals in the same subshell decrease with increase in the atomic number
(Zeff). For example, energy of 2s orbital of hydrogen atom is greater than that of 2s
orbital of lithium and that of lithium is greater than that of sodium because as number of
protons increases effective nuclear attraction increases.
Filling of Orbitals in Atom:
Aufbau Principle: In the ground state of the atoms, the orbitals are filled in order
of their increasing energies.
Electrons first occupy the lowest energy orbital available to them and enter higher
energy orbitals only after the lower energy orbitals are filled. Energy of a given orbital
depends upon effective nuclear charge and different type of orbitals are affected to
different extent.
Order of energies of the orbitals: 1s, 2s, 2p, 3s, 3p, 4s, 3d, 4p, 5s, 4d, 5p, 4f, 5d, 6p, 7s...
Pauli Exclusion Principle: No two electrons in an atom can have the same set of
four quantum numbers.
The maximum number of electrons in the shell with principal quantum number n is
equal to 2n2.
Hund’s Rule of Maximum Multiplicity: pairing of electrons in the orbitals
belonging to the same subshell (p, d or f) does not take place until each orbital
belonging to that subshell has got one electron each.
Electronic Configuration of Atoms: The distribution of electrons into orbitals of an
atom is called its electronic configuration.
The electrons in the completely filled shells are known as core electrons and the
electrons that are added to the electronic shell with the highest principal quantum
number are called valence electrons.
Half-filled and fully filled degenerate set of orbitals acquire extra stability due to their
symmetry.
Stability of Completely Filled and Half-Filled Subshells
Symmetrical distribution of electrons
Exchange Energy