Heisenberg’s Uncertainty Principle

It states that it is impossible to determine simultaneously, the exact position and exact
momentum (or velocity) of an electron
Mathematically, it can be given as in equation (2.23)—

where ∆x is the uncertainty in position and ∆px (or ∆vx) 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 [∆(vx ) is large]. On the other
hand, if the velocity of the electron is known precisely (∆(vx ) is small), then the position of
the electron will be uncertain (∆x will be large). Thus, if we carry out some physical
measurements on the electron’s position or velocity, the outcome will always depict a fuzzy
or blur picture.

Significance of Uncertainty Principle

1. It rules out existence of definite paths or trajectories of electrons and other similar
particles:
The trajectory of an object is determined by its location and velocity
at various moments. If we know where a body is at a particular instant and if we also know
its velocity and the forces acting on it at that instant, we can tell where the body would be
sometime later.
it is not possible to talk of the trajectory of an electron.
2. The effect of Heisenberg Uncertainty Principle is significant only for motion of microscopic
objects and is negligible for that of macroscopic objects.

This can be seen from the following examples. If uncertainty principle is applied to an object
of mass, say about a milligram (10^-6 kg), then
The value of ∆v∆x obtained is extremely small and is insignificant. Therefore, one may say that in
dealing with milligram-sized or heavier objects, the associated uncertainties are hardly of any real
consequence.

In the case of a microscopic object like an electron on the other hand. ∆v.∆x obtained is
much larger and such uncertainties are of real consequence. For example, for an electron
whose mass is 9.11×10^–31 kg., according to Heisenberg uncertainty principle

It, therefore, means that if one tries to find the exact location of the electron, say to an
uncertainty of only 10–8 m, then the uncertainty ∆v in velocity would be

which is so large that the classical picture of electrons moving in Bohr’s orbits (fixed) cannot
hold good. It, therefore, means that the precise statements of the position and
momentum of electrons have to be replaced by the statements of probability, that the
electron has at a given position and momentum. This is what happens in the quantum
mechanical model of atom.
 QUANTUM MECHANICAL MODEL OF ATOM
Quantum mechanics is based on Schrödinger’s wave equation and its solution. The solution
of the wave equation brings the idea of shells, sub-shells and orbitals. The probability of
finding an electron at a point within an atom is proportional to the |ψ|2 at that point, where
ψ represents the wave-function of that electron.
Application of Schrödinger’s equation to multi-electron atoms present’s some difficulty:
Schrödinger’s wave equation cannot be solved exactly for a multi-electron atom. This
difficulty was overcome by using approximate methods.
The application of Schrödinger wave equation in determining the structure of an atom led to
the formation of the quantum mechanical model of an atom.

• 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

A large number of orbitals are possible in an atom. Qualitatively these orbitals can be
distinguished by their size, shape and orientation. An orbital of smaller size means there is
more chance of finding the electron near the nucleus. Similarly shape and orientation mean
that there is more probability of finding the electron along certain directions than along
others.

Atomic orbitals are precisely distinguished by what are known as quantum numbers. Each
orbital is designated by three quantum numbers labelled as n, l and ml.

The principal quantum number ‘n’ is a positive integer with value of n = 1,2,3....... The
principal quantum number determines the size and to large extent the energy of the orbital.
For hydrogen atom and hydrogen like species (He+, Li2+, .... etc.) energy and size of the
orbital depends only on ‘n’. The principal quantum number also identifies the shell.

• Size of an orbital increases with increase of principal quantum number ‘n’.

Azimuthal quantum number. ‘l’ is also known as orbital angular momentum or subsidiary
quantum number. It defines the three-dimensional shape of the orbital. For a given value of
n, l can have n values ranging from 0 to n – 1, that is, for a given value of n, the possible
value of l are : l = 0, 1, 2, .......... (n–1)

For example, when n = 1, value of l is only 0. For n = 2, the possible value of l can be 0 and 1.
For n = 3, the possible l values are 0, 1 and 2.

Magnetic orbital quantum number. ‘ml ’ gives information about the spatial orientation of
the orbital with respect to standard set of co-ordinate axis. For any sub-shell (defined by ‘l’
value) 2l+1 values of ml are possible and these values are given by: ml = – l, – (l –1), – (l–2)...
0,1... (l –2), (l–1), l
 Thus for l = 0, the only permitted value of ml = 0, [2(0)+1] = 1, one’s orbital]. For l = 1, ml
can be –1, 0 and +1 [2(1)+1] = 3, three p orbitals]. For l = 2, ml = –2, –1, 0, +1 and +2,
[2(2)+1] = 5, five d orbitals]. . It should be noted that the values of ml are derived from l and
that the value of l are derived from n.

Electron spin quantum number (ms). An electron spins around its own axis, much in a
similar way as earth spins around its own axis while revolving around the sun .

The spin quantum numbers ms which can take the values of +½ or –½. These are called the
two spin states of the electron and are normally represented by two arrows, ↑ (spin up)
and ↓ (spin down).
Energies of the orbitals in the same subshell decrease with increase in the atomic number
(Zeff).

Filling of Orbitals in Atom

The filling of electrons into the orbitals of different atoms takes place according to the
aufbau principle which is based on the Pauli’s exclusion principle, the Hund’s rule of
maximum multiplicity and the relative energies of the orbitals.

Aufbau Principle:

The word ‘aufbau’ in German means ‘building up’. The building up of orbitals means the
filling up of orbitals with electrons. The principle states: In the ground state of the atoms,
the orbitals are filled in order of their increasing energies.

In other words, electrons first occupy the lowest energy orbital available to them and enter
into higher energy orbitals only after the lower energy orbitals are filled.
The order may be remembered by using the method given in Fig.

Pauli Exclusion Principle:

According to this principle : No two electrons in an atom can have the same set of four
quantum numbers. Pauli exclusion principle can also be stated as : “Only two electrons
may exist in the same orbital and these electrons must have opposite spin.” This means
that the two electrons can have the same value of three quantum numbers n, l and ml , but
must have the opposite spin quantum number.

For example, subshell 1s comprises one orbital and thus the maximum number of electrons
present in 1s subshell can be two, in p and d subshells, the maximum number of electrons
can be 6 and 10 and so on. This can be summed up as : the maximum number of electrons
in the shell with principal quantum number n is equal to 2n^2.

Hund’s Rule of Maximum Multiplicity: This rule deals with the filling of
electrons into the orbitals belonging to the same subshell Fig.2.17 Order of
filling of orbitals (that is, orbitals of equal energy, called degenerate orbitals).
It states: 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 i.e.,
it is singly occupied. Since there are three p, five d and seven f orbitals, therefore, the
pairing of electrons will start in the p, d and f orbitals with the entry of 4th, 6th and 8th
electron, respectively. It has been observed that half filled and fully filled degenerate set
of orbitals acquire extra stability due to their symmetry.

Wave mechanics: de Broglie equation:

The de Broglie equation is one of the equations that is commonly used to define the wave
properties of matter. It basically describes the wave nature of the electron.
Electromagnetic radiation, exhibit dual nature of a particle (having a momentum) and wave
(expressed in frequency, wavelength). Microscopic particle-like electrons also proved to
possess this dual nature property.
Louis de Broglie in his thesis suggested that any moving particle, whether microscopic or
macroscopic will be associated with a wave character. It was called ‘Matter Waves’. He
further proposed a relation between the velocity and momentum of a particle with the
wavelength, if the particle had to behave as a wave.

de Broglie Equation Derivation and de Broglie Wavelength:

Plank’s quantum theory relates the energy of an electromagnetic wave to its

wavelength or frequency.
E = hv

Einstein related the energy of particle matter to its mass and velocity, as E = mc2……..(2)
As the smaller particle exhibits dual nature, and energy being the same, de Broglie equated
both these relations for the particle moving with velocity ‘v’ as,

This equation relating the momentum of a particle with its wavelength is de Broglie
equation and the wavelength calculated using this relation is de Broglie wavelength.