Atomic Line Width

It is taken for granted that an atomic line should have infinitesimally small (or zero)
line width since transition between two quantum states requires an exact amount of
energy. However, careful examination of atomic lines reveals that they have finite
width. For example, try to look at the situation where we expand the x-axis
(wavelength axis) of the following line:

The effective line width in terms of wavelength units is equal to 1/2 and is defined as
the width of the line, in wavelength units, measured at one half maximum signal (P).
The question which needs a definite answer is what causes the atomic line to become
broad?

Reasons for Atomic Line Broadening

There are four reasons for broadening observed in atomic lines. These include:
1. The Uncertainty Principle
We have seen earlier that Heisenberg uncertainty principle suggests that nature places
limits on the precision by which two interrelated physical quantities can be measured.
It is not easy, will have some uncertainty, to calculate the energy required for a
transition when the lifetime of the excited state is short. The ground state lifetime is
long but the lifetime of the excited state is very short which suggests that there is an
uncertainty in the calculation of the transition time. We have seen earlier that when we
are to estimate the energy of a transition and thus the wavelength (line width), it is

required that the two states where a transition takes place should have infinite
lifetimes for the uncertainty in energy (or wavelength) to be zero:
E>h/t
Therefore, atomic lines should have some broadening due to uncertainty in the
lifetime of the excited state. The broadening resulting from the uncertainty principle is
referred to as natural line width and is unavoidable.
2. Doppler Broadening
The wavelength of radiation emitted by a fast moving atom toward a transducer will
be different from that emitted by a fast atom moving away from a transducer. More
wave crests and thus higher frequency will be measured for atoms moving towards the
transducer. The same occurs for sound waves. Assume your ear is the transducer,
when a car blows its horn toward your ear each successive wave crest is emitted from
a closer distance to your ear since the car is moving towards you. Thus a high
frequency will be detected. On the other hand, when the car passes you and blows its
horn, each wave crest is emitted at a distance successively far away from you and
your ear will definitely sense a lower frequency.

The line width () due to Doppler broadening can be calculated from the relation:
/ o = v/c
Where o is the wavelength at maximum power and is equal to (1 + 2)/2, v is the
velocity of the moving atom and c is the speed of light. It is noteworthy to indicate
that an atom moving perpendicular to the transducer will always have a o, i.e. will
keep its original frequency and will not add to line broadening by the Doppler effect.

In the case of absorption lines, you may visualize the line broadening due to
Doppler effect since fast atoms moving towards the source will experience more wave
crests and thus will absorb higher frequencies. On the other hand, an atom moving
away from the source will experience less wave crests and will thus absorb a lower
frequency.
The maximum Doppler shifts are observed for atoms of highest velocities moving in
either direction toward or away from a transducer (emission) or a source (absorption).
3. Pressure Broadening
Line broadening caused by collisions of emitting or absorbing atoms with other
atoms, ions, or other species in the gaseous matrix is called pressure
or collisional broadening. These collisions result in small changes in ground state
energy levels and thus the energy required for transition to excited states will be
different and dependent on the ground state energy level distribution. This will
definitely result in important line broadening. This phenomenon is most astonishing
for xenon where a xenon arc lamp at a high pressure produces a continuum from 200
to 1100 nm instead of a line spectrum for atomic xenon. A high pressure mercury
lamp also produces a continuum output. Both Doppler and pressure contribution to
line broadening in atomic spectroscopy are far more important than broadening due to
uncertainty principle.
4. Magnetic Effects
Splitting of the degenerate energy levels does take place for gaseous atoms in
presence of a magnetic field. The complicated magnetic fields exerted by electrons in
the matrix atoms and other species will affect the energy levels of analyte atoms. The
simplest situation is one where an energy level will be split into three levels, one of
the same quantum energy and one of higher quantum energy, while the third assumes
a lower quantum energy state. A continuum of magnetic fields exists due to complex
matrix components, and movement of species, thus exist. Electronic transitions from
the thus split levels will result in line broadening.

ANALYTICAL CHEMISTRY
ATOMIC SPECTROMETRY

COURSE CODE: CHEM-4103

NAME: Muhammad Abdullah Khan
ROLL # 161-BH-CHEM-12

INSTRUCTOR: Professor Dr. Islam-Ullah

Khan