ATOMIC STRUCTURE

What is an atom?

Atoms are the building blocks of all matter. They are extremely small and
atomic radius is measured in units of nanometer.

John Daltons atomic theory provided an explanation for the law of

conservation of mass and the law of definite proportions.

According to Daltons atomic theory:

All matter is made up of very tiny particles called atoms

Atoms are indivisible particles which cannot be created or destroyed
Atoms of a given element are identical in mass and chemical
properties.
Atoms combine in the ratio of small whole numbers to form
compounds.
Atoms of different elements have different masses and chemical
properties.
The relative number and kinds of atoms are constant in a given
compound.
Drawbacks:
But, the discovery of two fundamental particles; electrons and protons
inside the atom led to the failure of Daltons atomic theory.

J.J.Thomson was the first scientist to propose a model for the structure of an
atom.

Thomsons model of an atom

Thomson proposed that

An atom consists of a positively

charged sphere and the electrons are
embedded in it.
The negative and positive charges are
equal in magnitude.
Mass of the atom is assumed to be uniformly distributed over the
atom.

Drawbacks:
 Although this model explained that atoms are electrically neutral, it failed
to explain the scattering experiment.

Rutherfords nuclear model of an atom.

Rutherfords scattering experiment : when a beam of particles is shot at

a thin gold foil most of them passed through the gold foil undeflected, some
particles were deflected by small angles and a very few particles were
bounced back by nearly 1800

Through this Rutherford explained that

Most of the space inside the atom is empty because most of the alpha
particles passed through the gold foil without getting deflected.
Very few particles were deflected from their path indicating that
positive charge of atom occupies very little space.
A very small fraction of alpha particles were deflected by 180 degrees
indicating that all positive charge and mass of the gold atom were
concentrated in a small volume within the aotm.

On this basis of this Rutherford proposed the nuclear model of an atom.

According to this model

The positive charge and most of the mass of the atom was densely
concentrated in extremely small region called nucleus.
The nucleus is surrounded by electrons that move around it with a
high speed in circular path called orbits.
Electrons and nucleus are held together by electrostatic forces of
attraction.

Drawbacks :

The orbital revolution of the electron is not expected to be stable as any

particle in a circular motion would undergo acceleration and radiate energy.
Thus the electron would lose energy and fall into the nucleus and due to this
atom would be highly unstable. But atoms are quite stable. Also it says
nothing about the electronic structure of atoms.

BOHRs model of atom

Two developments played a major role in the formulation of Bohrs model

of an atom. These
were:

Dual character of
the
electromagnetic
radiation which
means that
radiations
possesses both
wave like and
particle like
properties.
Experimental
results regarding atomic spectra which can be explained only by
assuming quantized electronic energy levels in atom.

Wave nature of electromagnetic radiation:

James Maxwell suggested that when an electrically charged particle moves

under acceleration , alternating electrical and magnetic fields are produced
and transmitted in the form of waves known as electromagnetic radiation.

Electromagnetic waves do not require a medium and can move in vacuum.

There are many types of electromagnetic radiation which differ from one
another in wavelength. This constitutes the electromagnetic spectrum.

Particle nature of electromagnetic radiation (Plancks quantum

theory):

Planck gave the name quantum to the smallest quantity of energy that can
be emitted or absorbed in the form of electromagnetic radiation. E=h where
E is energy, h is Plancks constant and is frequency. The value of h is 6.626
x 10 -34 Js
With this theory Planck was able to explain the distribution of intensity in the
radiation from black body as a function of frequency or wavelength at
different temperatures.

Photoelectric effect : When Hertz performed an experiment in which

electrons were ejected when certain metals Potassium, Rubidium, Caesium
etc were exposed to a beam of light, the results observed were as follows:

The electrons are ejected from the metal surface as soon as the beam
of light strikes the surface.
The number of electrons ejected is proportional to the intensity of the
light.
For each metal there is a threshold frequency below which
photoelectric effect is not observed. At a frequency of v>vo the ejected
electrons come out with certain kinetic energy which increases with
the increase of frequency of light used.

BOHRs model for Hydrogen atom

Neil Bohrs model for hydrogen is

based on the following postulates.
The electron in the hydrogen
atom can move around in
the nucleus in a circular path
of fixed radius and energy
called orbit. These orbits are
arranged concentrically
around the nucleus.
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 an electron moves from higher
stationary state to lower stationary state.

Bohrs frequency rule : =E/h = E2-E1/h where E1 and E2 are

the energies of lower and higher allowed energy states. The
angular momentum of an electron at a given stationary state can
be expressed as an equation
mevr = n.h/2
thus an electron can move only in those orbits for which its
angular momentum is integral multiple of h/2
 Limitations of Bohrs model:
It fails to explain spectrum other than hydrogen and the
splitting of spectral lines in the presence of magnetic and
electrical field .
It could not explain ability of atoms to form molecules .

Quantum mechanical model of the atom :

Two developments contributed towards quantum model were:

Dual behavior of matter
De Broglie proposed that matter exhibits particle and wave like
properties.
=h/mv=h/p where m is the mass of the particle,v is the velocity ,p
is the momentum.

Heisenberg uncertainty principle

Heisenberg principle states that
It is impossible to determine simultaneously the exact position and
momentum of an electron.

Important features of quantum mechanical model

1. Energy of electrons in atoms is quantized.
2. The existence of quantized electronic energy levels is direct result of
the wave like properties of electrons.
3. Both the exact position and the exact velocity of an electron cannot be
determined simultaneously.
4. An atomic orbital is the wave function for an electron in an atom.
5. The probability of finding an electron at a point within an atom is
proportional to the square of orbital wave function.

Orbitals and quantum numbers

There are four types of quantum numbers. They are:

Principal quantum numbers

Azimuthal quantum numbers
Magnetic quantum numbers
Spin quantum numbers
Principal quantum numbers:

It is represented with the letter n.

It is a positive integer with value n=1,2,3.

The principle quantum number determines the size and energy of the
orbital. With the increase in the value of n, number of orbital increases.

Azimuthal quantum number:

It is represented with the letter l.

It is also known as orbital angular momentum or subsidiary quantum
number.
It defines the 3d shapes of orbitals.
For a given value of n l can have values ranging from 0 to-1.
Each shell consists of 1 or more subshells or sub-levels.
The number of subshells is equal to the value of n.
Each subshell is assigned an azimuthal quantum number.

Magnetic orbital quantum number:

It gives the special orientation of the orbit with respect to standard set
of coordinate axis.
For any subshell 2l+1 values of m are possible.

Each orbital is defined by a set of values nl and m.

Electron spin quantum number:

An electron has, besides charge and mass, an intrinsic spin angular quantum
number which is a vector quantity having two orientations representing two
spin states spin up and spin down represented by m.

Conclusion: Orbit, orbital and its importance:

Orbit and orbital are not synonymous. An orbit as proposed by Bohr is a
circular path around the nucleus in which an electron moves. A precise
description of this path of the electron is impossible according to
Heisenbergs uncertainty principle. Bohr orbits therefore have no real
meaning and their existence can never be demonstrated experimentally.
An atomic orbital on the other hand is a quantum mechanical concept and
refers to one electron wave function in an atom. It is characterized by
three quantum numbers and its value depends upon the coordinates of the
electron. has by itself no physical meaning. It is the square of wave
function that is || 2. which has a physical meaning. || 2 at any point in an
atom gives the value of probability density at that point. Probability density
(|| 2 ) is the probability per unit volume and the product of || 2 and a small
volume yields the probability of finding the electron in that volume calculated
by sum of all the products of || 2 and the corresponding volume elements.
It is thus possible to get the probable distribution of an electron in an orbital.

Shapes of atomic orbital

According to Max Born the square of wave function at a point gives the
probability density of the electron at that point.
It has been found that ns-orbital has n-1 nodes that is number of nodes
increases with the increase of principle quantum number n.
Boundary surface diagrams of constant probability density for different
orbital gives a good representation of the shapes of the
orbital. Boundary surface diagram for an s orbital is actually
a sphere centered on the nucleus. In two dimension the
sphere looks like a circle. Thus we see that 1s and 2s orbitals
are spherical in shape.
Boundary surface diagram for the three 2p orbitals are shown
in the figure right.
These consists of two lobes on either side
of the plane.

The 5 d-orbitals is shown in the figure left. Shapes of

first 4 d-orbitals are similar where as the fifth one is
different, but all the five are equal in energy.

Energies of orbitals
The energy of an electron in a hydrogen atom is determined by the principal
quantum number. The orbitals having the same energy are called
degenerate. The 1s orbital in a hydrogen atom corresponds to the most
stable condition and is called the ground state and an electron residing in
this state is more strongly held by the nucleus. The energy of an electron in
a multi electron atom depends not only on its principal quantum number
(shell) but also on its azimuthal quantum number (sub shell). The main
reason for having different energies of the sub shell is the mutual repulsion
among the electrons. The repulsive interaction in the outer shells with the
electrons in the inner shell is important. On the other hand the attraction
interactions of an electron increase with the positive charge (Ze) on the
nucleus. Despite the shielding of the outer electrons from the nucleus by the
inner shell electrons the attractive force experienced by the outer shell
increases with the increase in nuclear charge. Thus the energy of interaction
between nucleus and electron decreases with the increase in atomic number.
The attraction and repulsion forces depends on the shell and shape of the
orbital in which the electron is present. The s orbital electron will be more
tightly bound to the nucleus than the 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 than that of p orbital electron which will have less
energy than d electron. Since the extent of shielding from the nucleus is
different for electron in different orbitals, it leads to splitting of energy levels
within the same shell. The dependence of energies of the orbitals on n and l
is based on one simple rule: The lower the value of (n+l) for an orbital, the
lower is its energy. If two orbitals have the same value of (n+l), the orbital
with the lower value of n will have the lower energy. Energies of the orbitals
in the same subshell decreases with the increase in the atomic number.

Filling of orbitals in atom

The filling of electrons into the orbitals of different atoms takes place
according to Aufbau principle which is based on Paulis exclusion principle,
Hunds rule of maximum multiplicity and the relative energies of the orbitals.

Aufbau Principle states that In the ground state of the atoms, the orbitals
are filled in order of their increasing energies. The order in which the
energies of the orbitals increase and hence the order in which the orbitals
are filled is as follows:
1s,2s,2p,3s,3p,4s,3d,4p,5s,4d,5p,4f,5d,6p,7s..

Pauli Exclusion Principle: According to this principle no two electrons in

an atom can have the same set of four quantum numbers. Only two
electrons may exist in the same orbital and these electrons must have
opposite spin. This restriction helps in calculation of the capacity of electrons
to be present in a subshell. The maximum number of electrons in the shell
with principal quantum number n is equal to 2n2.

Hunds rule of maximum multiplicity states that pairing of electrons in

the orbitals belonging to the same subshell(p,d or f) does not take place
until each electron belonging to that sub shell has got one electron each.

Electronic configuration of atoms:

The distribution of electrons into orbits of an atom is called its electronic

configuration. This can be represented in two ways:
 Sa pb dcnotation where S, p, d are subshells and a,b,c are number of
electrons present in the sub shell. The principal quantum number is
written before the sub shell.
Orbital diagram where each orbital of the sub shell is represented by a
box and the electron is represented by arrow spin. Advantage is that it
represents all four quantum numbers.

Electrons in completely filled shells are known as core electrons and

electrons that are added to the electronic shell with the highest principle
quantum number are called valence electrons.

The modern approach to chemistry depends entirely on electronic

distribution to understand and explain chemical behavior.