Absorption and emission processes

E2 2
a absorption
a b c b spontaneous emission
c stimulated emission
E1 1

Absorption
Molecule absorbs a quantum of radiation M + h → M*
(a photon) and is excited from 1 to 2. (state 1) (state 2)

Spontaneous emission
M* (in state 2) spontaneously emits a M * → M + h
photon of radiation.

Stimulated emission
A quantum of radiation is required to M * + h → M + 2h
stimulate M* to go from 2 to 1.
 LASER SPECTROSCOPY

Lecture 1 - Basics of laser systems

• Absorption and Emission processes.
• Conditions for laser action.
• Properties of laser radiation.
• Real Laser Systems.

Recommended reading - not buying!

• High Resolution Spectroscopy/Modern Spectroscopy by J.M.Hollas.
• An Introduction to Lasers and their Applications by O’Shea, Callen and
Rhodes.
• Laser Electronics by Verdeyen.
Rates of absorption and emission processes

• Rates are determined by the Einstein coefficients for each process

dN 1
= N1B12  ( ) Absorption () is the energy density of
dt
the incident radiation and
dN 2
= N 2 B21  ( ) Stimulated emission N1 and N2 are the
dt populations of states 1 and 2
dN 2
= N 2 A21 Spontaneous emission respectively.
dt

Under thermal conditions the population of two states 1 and 2, is determined

by the Boltzman distribution.

N2  − E 
= exp 
N1  kT 

Where E is the energy difference between the two states, T is the

temperature and k is Boltzmans constant.
Stimulated and spontaneous emission

Spontaneous emission
• Photons emitted in all directions and on a random time scale.
• The emitted photons are INCOHERENT

Stimulated emission
• Emitted and stimulating photons have the same :
• Frequency
• Direction
• Phase
• The emitted and incident photons are COHERENT
First condition for laser action

If N1 > N2
• If most molecules in state 1, then incoming radiation is mainly absorbed.
• Incident radiation is attenuated (reduced).
If N2 > N1
• If most molecules are in state 2, absorption of incoming radiation is hindered.
• The result is stimulated emission.
• Incident radiation is amplified.

Thus for laser action require a population inversion, N2 > N1

 How to obtain a population inversion

Consider the Boltzman equation.

N2  − E 
= exp 
N1  kT 
When kT is large, the ratio of N2/N11, equal numbers of molecules in
state 1 and state 2.
When kT is small the ratio of N2/N1  0 and all molecules are in state 1.

Cannot obtain a population inversion using thermal methods in a 2 level system.

• Multi-level systems must be employed.

• Molecules need to be pumped into a higher energy state.

Various methods : electrical discharge, flashlamp excitation.

• Continuous pumping gives a Continuous Wave (CW) Laser.
• Pulsed pumping gives a Pulsed Laser (PL) output.
 Population Inversion

Example of a 3 level system

E3 Rapid decay
E2

LASING

E1
• 1→3 transition is pumped.
• Rapid decay from 3 →2.
• State 2 is metastable, excited molecules can remain in state 2 for an
extended time period, population of state 2 builds up.
• Decay from state 3 means absorption from 1 →3 is favoured, creating
population inversion between 2 and 1.
• Laser action is possible between states 2 and 1.
Population Inversion

Example of a 4 level system

E4
Rapid decay
E3
LASING
E2
Rapid decay
E1
• 1→4 transition is pumped.
• Rapid decay from 4 →3.
• A population inversion is produced between states 3 and 2.
• Laser action is therefore possible between 3 →2.
• Molecules decay rapidly from 2 →1, replenishing population of 1.
 Laser Gain

The amount of amplification of the incident beam in a single pass is small,

a fraction of a percent/centimetre of travel.
To increase the path length through the sample could use either:
• A very long laser/gain medium.
• Mirrors to reflect the beam back into the sample.

mirror gain medium mirror

• The gain medium is the substance which can support the population
inversion, can be solid, liquid or gas.
• The combination of the gain medium and the mirrors is called the laser
cavity or the optical resonator.
 Basics of a complete laser system
• The gain medium is pumped by some method.
• Some of the atoms/molecules are excited.
• Spontaneous emission occurs, in all directions.
• Emission along long axis of cavity is reflected back through the gain
medium.
• The spontaneously emitted photons stimulate further emission from
the medium.
• A large radiation density quickly builds up.

LASING

mirror gain medium mirror mirror gain medium mirror

• One of the mirrors is usually partially transmitting to allow some of the

laser radiation to escape.
 Summary of requirements for laser action

EXCITER

energy

GAIN MEDIUM LASER OUTPUT

OPTICAL RESONATOR

The three components required for laser action are:

• A gain medium which can support a population inversion.
• An external exciter to create the population inversion in the gain medium.
• An optical resonator or cavity to create a high radiation density.

The various types of lasers differ in the types of gain medium, external
exciter and size and type of cavity employed.
Ruby Laser

• Invented in the 60’s, was the first proper laser.

• The gain medium is a crystal of Ruby, which is an aluminium oxide
crystal with some of the aluminium atoms replaced with chromium.

• The excitation of the ruby crystal is obtained by a flashlamp spiralled

around the crystal.
• Mirrors at each end of the crystal form the cavity.
 Ruby Laser

• The lasing constituents of the Ruby crystal are the Cr3+ ions, present in
low concentration.
• The laser action follows that of a 3 level system.

• Pump either the 4T1 or 4T2 states,

use 510-600nm or 360-450nm
4T
1 radiation respectively.
2T
2
• Each decays to the metastable 2E
state.
Energy

rapid decay • Laser action occurs from 2E to

4T 4A with a frequency of 694 nm.
2 2,
2E

LASING
4A
2
Gain Media

• Can be a solid, liquid or gas.

Name Gain Medium Lasing Wavelength Uses
Nd:YAG Neodinium ions in a 1064nm, can be Pump source for dye
yitrium aluminium frequency doubled to lasers, spectroscopy,
garnet crystal. 532nm, 355nm etc. desorption.
Ruby Chromium ions in 694 nm (red) Medical applications,
aluminium oxide eg. Tattoo repoval.
crystal.
Helium Neon Helium Neon gas 632 nm Usually low power,
mixture Laser Pointers
Carbon CO2, N2, He and CO 10.6 m Very high power,
dioxide mixture desorption, laser
cutting, laser etching.
Dye Lasers Organic dyes, e.g. Range of Spectroscopic
Rhodamines and 200nm→1000nm applications mainly.
Coumarins
 Properties of laser output

Output is intense and coherent.

The linewidth (spread of frequencies) of the laser beam is determined by
several factors:

• Doppler broadening (gases, liquids).

• Collisional broadening (gases, liquids, also solid state,due to crystal
•interactions).
• Natural linewidth of the lasing transition (uncertainty principle).
• Number of modes active in the cavity.

The linewidth of most lasers is still of the order of a wavenumber or less,

sufficient for most spectroscopic applications.

To achieve very narrow line widths (for rotational spectroscopy) optical

components can be inserted into the cavity to narrow the number of modes
which are active, or to favour a single mode.
The Optical resonator

• The size and quality of the cavity are crucial for successful laser action.
• To support lasing the length of the cavity (L) must be and integral (n)
number of half wavelengths (/2).
 
L = n 
2

(This is the condition for constructive interference.)

• For each cavity, many modes can satisfy this resonance condition.
• Laser output is, therefore, composed of a spread of frequencies.
The Optical resonator

The Quality or Q-factor of a laser cavity is essentially a measures the

ability of a laser cavity to store energy.
The Q factor can be related to the energy stored in the cavity Ec, and the
amount lost, Et, by the following equation.
2Ect
Q=
Et
Every laser cavity must have some loses due to the partially reflective
nature of the cavity mirrors.
Q-switching is a method of producing short pulses of very high energy in
pulsed laser systems.

Q-switching is often achieved by having shutters or a saturatable absorber in

the cavity.
Tunablity of wavelength.

Most lasers emit a single, or several discrete frequencies of radiation.

However, for many spectroscopic applications wavelength tunability is
necessary.
Solution is to use a dye laser pumped by a fixed frequency laser.
The gain medium is an organic dye, which has a broad emission and
absorption profile.
• Population inversion occurs
between v`=0 in S1 and v``=n in S0.
• Emission frequency selected by a
diffraction grating.
• Used to stimulate further emission
from amplifier dye cells.
LASING