LASERS OSPL Department – BUCHAREST UNIVERSITY OPTICS

SPECTROSCOPY
&
LASERS

SPECTROSCOPY
Lecturer Dr. Iulian Ionita

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LASERS OSPL Department – BUCHAREST UNIVERSITY OPTICS

How important is spectroscopy?

What is a spectrum and how can we

measure it?
Spectral instrumentation.
Spectroscopy and evolution of quantum
idea!

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Atomic spectra.

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LASERS OSPL Department – BUCHAREST UNIVERSITY OPTICS

How important is spectroscopy?

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LASERS OSPL Department – BUCHAREST UNIVERSITY OPTICS

Conclusions:
1. The sight provides us information
about matter
2. from longer distance than any other
sense.
3. To have a correct information we need
to calibrate it!

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LASERS OSPL Department – BUCHAREST UNIVERSITY OPTICS

PHOTONICS =
technology using photons:
- Light sources
- Displays
- Photodetectors
- Telecommunications
- Memory devices (data storage)
- Analyze techniques

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- Imaging techniques
- Computers
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LASERS OSPL Department – BUCHAREST UNIVERSITY OPTICS

PHOTONICS =

- Optics: propagation of light

- Spectroscopy: nature of light
- Lasers: special light

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Most of what we know about the universe comes from studying the
interaction of light and matter, which makes spectroscopy a
fundamental technique in understanding the world around us.
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LASERS OSPL Department – BUCHAREST UNIVERSITY OPTICS

The LASE Plenary at Photonics West hosted the father of the laser, Nobel laureate
Charles Townes, on Wednesday 24 January 2008. Townes explained the origins of the
first laser (actually a maser), derived from his work on microwave spectroscopy of
molecules.
Clearly, the laser has evolved considerably since 1954, and laser technology is now
ubiquitous in modern life. For Townes, this highlighted how the results of basic research
can contain immense unexpected benefits. He commented that industry and government
politicians need to see that the long-term payoff potential of basic research extends well
beyond the next fiscal cycle. Townes also discussed how rapidly the development of the
laser progressed once the initial ideas were circulated, showing the overall importance of
community to the development of new technology.
Another theme of Townes's talk was his illustration of how new ideas are often resisted by
the acknowledged experts in the field. Townes related how many scientists, among
them Niels Bohr and his department chairs at Columbia, thought that the laser was
theoretically impossible. Even the Bell Labs patent office refused to entertain a
patent on the laser because it lacked a direct application to communications.
Scientists and representatives of the multi-million dollar laser industry honored Townes

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with a plaque and a lengthy standing ovation for his work on the laser and contributions
to science. When asked what fields might be ripe for a breakthrough like the laser,
Townes knowingly answered, "all of them," but identified biophysics, nanotechnology, and
negative index of refraction materials as holding special promise.
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LASERS OSPL Department – BUCHAREST UNIVERSITY OPTICS

What is a spectrum?

Spectrum is a relationship between INTENSITY and ENERGY.

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LASERS OSPL Department – BUCHAREST UNIVERSITY OPTICS

History of Spectroscopy
L. spectrum - an appearance, an apparition, from spectare, to
behold
G. skopein - to view
Spectroscopy is used to determine identity, quantity, structure, and
the environment of atoms, molecules, and ions by analyzing the
radiation emitted or absorbed by atoms, molecules, or ions.
Optical spectroscopy is concerned with transitions of valence
electrons.
X-ray spectroscopy is concerned with the transition of inner-core
electrons.
Nuclear magnetic spectroscopy is concerned with transitions

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involving the nucleus.
Mass spectrometry involves the separations of ions based on their
mass.
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LASERS OSPL Department – BUCHAREST UNIVERSITY OPTICS

One thing that you need to remember is that "light" is a lot more than
just the colored visible light that we can see. In addition to the
traditional "ROY G. BIV" (Red, Orange, Yellow, Green, Blue, Indigo,
Violet) color spectrum, there are gamma rays, x-rays, ultraviolet
(UV) radiation, infrared (IR) radiation, microwaves and radio waves!

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"ROGVAIV"
(Roşu, Orange, Galben, Verde, Albastru, Indigo, Violet)

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LASERS OSPL Department – BUCHAREST UNIVERSITY OPTICS

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LASERS OSPL Department – BUCHAREST UNIVERSITY OPTICS

How can we make spectral analyses?

It is possible to take the light that a material emits, absorbs,

or reflects, and separate it into its parts - just like a prism can
break white light up into the visible light spectrum. If you break up a
sample of light of all wavelengths, you get what's called a
continuous spectrum. Below is an example of a continuous
spectrum for visible light.

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LASERS OSPL Department – BUCHAREST UNIVERSITY OPTICS

How can we make spectral analyses?

• Something similar can be done across the full electromagnetic

spectrum using prisms made of different materials, or what are
called diffraction gratings. Devices that use these elements are
called spectrometers.
• When light is absorbed or reflected by materials, not all of the light
behaves the same. Only certain wavelengths of light get
absorbed, others get reflected. You may recall this from past
science classes - it's why a red object looks red!
• Some materials emit light without being hit by light first - another
energy source (for example, heat or electricity) is used instead to
first excite the material, and then that energy is turned into light.
For example, a common light bulb emits light when electricity is
passed through it.
• When you separate the light that is passing through a sample, or

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reflecting off a sample, you end up with an emission spectrum or
absorption spectrum, as opposed to the continuous spectrum you
would get if you break up a source of all wavelengths of light.

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LASERS OSPL Department – BUCHAREST UNIVERSITY OPTICS

An emission spectrum in the visible light range may look like the
picture below.
Such a spectrum would be created when material is given extra
energy somehow (it's heated, electrified, radiated with light, etc.)
and that extra energy is later emitted as light energy.

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LASERS OSPL Department – BUCHAREST UNIVERSITY OPTICS

If that light is separated into its component parts, you can

see the spectrum of the emission. In this case, only the
wavelengths of light which are emitted come out in the
spectrum.

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LASERS OSPL Department – BUCHAREST UNIVERSITY OPTICS

An absorption spectrum in the visible light range may look like the
picture below. Such a spectrum would be created when light is
passed through a gas or a liquid, or strikes a solid. Certain
wavelengths of light will be absorbed by the material, and later
emitted in random directions. Most of the wavelengths, however, will
pass through the gas or liquid (or be reflected off the solid) without
being absorbed.

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LASERS OSPL Department – BUCHAREST UNIVERSITY OPTICS

If the light that passes through (or reflects off) is then separated into
its component parts, you can see the spectrum of the absorption. In
this case, the wavelengths of light absorbed by the material are
absent in the spectrum, leaving blank spaces behind.

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LASERS OSPL Department – BUCHAREST UNIVERSITY OPTICS

Optical Prism and Characteristics

The Prism is an optical device which break white light into its components based
on dispersion phenomenon. It was the first way to make spectral separation of light, first
time reported by Newton.
2.1. Relationship of the optical prism
Dispersion means radiations with different wavelength have different velocities
in a medium. For a transparent medium we can define the refractive index which depends
on the wavelength like:

V G R
b
n a (Cauchy’s relationship)
 2

Fig.2.1

Because λred > λviolet then nR < nV and phase velocity vR > vV (n = c/v). When the
wavefront of the white light is normal incident on the surface of a transparent

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material, as consequence a difference between wavefront of red radiation and
wavefront of violet radiation will appear, which will increase for higher thickness of
the material (Fig. 2.1). This kind of separation of light components is not useful
because is not stationary (ultra-fast – femtosecond!).

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LASERS OSPL Department – BUCHAREST UNIVERSITY OPTICS

The stationary separation of light in colors is made by optical prism, which is composed by two flat dioptres,
making an angle called prism angle A or refraction angle. The relationships of optical prim are as follow:

sin i  n sin r δ
n sin r '  sin i '


i i’

 A  r  r'
r r’

  i  i ' A

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Fig. 2.2, i = incident angle, i’ = emerging angle, δ = deviation angle, n = refractive index of prism material.

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LASERS
OSPL Department – BUCHAREST UNIVERSITY OPTICS

It is a particular case called minimum deviation (when δ has the smallest value), which is
very important because optical aberrations are minimum in that case.
The Prism is in condition of minimum deviation if:
- light ray tracing has a symmetry (i = i’, r = r’) regarding the prism axes, or if
- light ray propagates parallel to the base prism, or in other words,
perpendicular to the prism angle bisector.
At minimum deviation the refraction relationship comes like:

A A
n sin  sin
2 2

Angle of minimum deviation depends on refractive index,

then on wavelength. If many light rays with different
wavelength are incident on the prism at the same angle then
they will be deviated at different angles, thus they will be R

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angular separated by the prism. Smaller wavelength more G
deviation!
V

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LASERS OSPL Department – BUCHAREST UNIVERSITY OPTICS

1. Angular Dispersion

d di'
Du  
d d i’
i
i’+di’

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LASERS OSPL Department – BUCHAREST UNIVERSITY OPTICS

2. Power of chromatic resolution

It is a measure of the prism capacity to make fine spectral lines.


R 100%

d 81%

d is the smallest resolvable wavelength

difference

 +d

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Rayleigh principle

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LASERS OSPL Department – BUCHAREST UNIVERSITY OPTICS

2. Power of chromatic resolution

i

D sin    A
di’

R  D  Du b

dn
R  b
dλ

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LASERS OSPL Department – BUCHAREST UNIVERSITY OPTICS

Chromatic dispersion of two standard materials used

for prism manufacturing
1 .7
n
quartz
1 .6 glass

1 .5

20 0 4 00 600 800
 (n m )

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LASERS OSPL Department – BUCHAREST UNIVERSITY OPTICS

Prism based spectral instruments

Dispersive Projection
Entrance slit Collimator element Objective Exit slit

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LASERS OSPL Department – BUCHAREST UNIVERSITY OPTICS

Entrance slit

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Light rays drawing in a prism spectrograph

Objective
Collimator
Photoplate
(detector)

Slit

Prism

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LASERS OSPL Department – BUCHAREST UNIVERSITY OPTICS

Monochromator
(Ebert configuration)

Spectrograph

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(Czerny-Turner configuration)

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LASERS OSPL Department – BUCHAREST UNIVERSITY OPTICS

1. Linear dispersion

dx
Dl 
d
+d

di’


di '
Dl  f   f  Du
d

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LASERS OSPL Department – BUCHAREST UNIVERSITY OPTICS

2. Luminosity (brightness)

2
D
  ct  2
f

Numerical Aperture NA

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NA = n*sinθ

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LASERS OSPL Department – BUCHAREST UNIVERSITY OPTICS

3. The shape of spectral lines

Fig. 2.19

P’ 1 2

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P

Fig. 2.21
Fig. 2.20

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LASERS OSPL Department – BUCHAREST UNIVERSITY OPTICS

Rutherford’s Prism Amici’s Prism

D A
E

B C
Fig. 2. 22 Fig. 2.23

Cornu’s Prism

dextrogir levogir

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a b
Fig. 2.24.

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LASERS OSPL Department – BUCHAREST UNIVERSITY OPTICS

Wodsworth’s mounting for monochromator

(at constant deviation)

Fig. 2.25

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LASERS OSPL Department – BUCHAREST UNIVERSITY OPTICS

First Spectrophotometer
•
• The Beckman DU was designed from the ground
up, including the hydrogen lamp, monochromator,
and UV-sensitive phototube, in only 14 months.

• Howard Cary, lead designer for the DU and the

Beckman G pH meter, later left Beckman
instruments to start his own company, Applied
Physics Corporation. The Cary 14, one of his
designs, is widely regarded as the finest
dispersive optical instrument ever made.

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LASERS OSPL Department – BUCHAREST UNIVERSITY OPTICS

Spectrophotometer
Beckman DU

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LASERS OSPL Department – BUCHAREST UNIVERSITY OPTICS

The light goes back to the collimating mirror and through

the sample before being collected in the phototube and
measured. The light passes through the slit again before
going the sample. This allows the absorbance at one
wavelength to be measured without interference from other
light.

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LASERS OSPL Department – BUCHAREST UNIVERSITY OPTICS

DIFFRACTION GRATING

Diffraction grating was first time used in spectral application by american astronom D.
Rittenhaus in 1786. It was made from hairs.
First theory of diffraction grating was made by Joseph von Fraunhofer, who suggested
manufacture of grating by scratching the glass with a diamond. He suggested also the
grating could operate by reflection.

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Rowland realized first machine to fabricate gratings by mechanical ruling.

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LASERS OSPL Department – BUCHAREST UNIVERSITY OPTICS

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LASERS OSPL Department – BUCHAREST UNIVERSITY OPTICS

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LASERS OSPL Department – BUCHAREST UNIVERSITY OPTICS

Grating Maxima Intensity Comparison

The grating intensity expression gives a peak intensity

which is proportional to the square of the number of slits
illuminated. Increasing the number of slits not only

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makes the diffraction maximum sharper, but also much
more intense.

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LASERS OSPL Department – BUCHAREST UNIVERSITY OPTICS

When the 632.8nm red light from a helium-neon laser strikes

a diffraction grating it is diffracted to each side in multiple
orders. Orders 1 and 2 are shown to each side of the direct

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beam.

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LASERS OSPL Department – BUCHAREST UNIVERSITY OPTICS

k=2 k=1
N d N k=0
A'  B' k=3
k=-1
A B k=-2


Fig. 1

The grating fundamental equation is given by:

sin   sin   kn

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k = m = diffraction order

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LASERS OSPL Department – BUCHAREST UNIVERSITY OPTICS

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LASERS OSPL Department – BUCHAREST UNIVERSITY OPTICS

Diffraction Grating

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The condition for maximum intensity is the same as that for a double slit.
However, angular separation of the maxima is generally much greater
because the slit spacing is so small for a diffraction grating.
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LASERS OSPL Department – BUCHAREST UNIVERSITY OPTICS

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White light incident on a reflection grating is diffracted: its component
wavelengths emanate in different directions. Note that there is also a white
reflected beam; the grating also acts as a mirror. The figure for a transmission
grating would show the reflected and diffracted light below the grating.

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LASERS OSPL Department – BUCHAREST UNIVERSITY OPTICS

Two common groove profiles (the grating is shown in cross-

section). (a) sinusoidal profile; (b) triangular ("blazed") profile

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LASERS OSPL Department – BUCHAREST UNIVERSITY OPTICS

Prism versus Grating

1. The grating produces many spectra. Zero order diffraction maximum is
not dispersed (always “white”). Radiation coming into the k = 1, 2, 3... Maxima is
dispersed. The prism has only one spectrum.
2. Based on fundamental grating equation, red radiation has a greater
deviation than violet one, contrary to the prism.
3. Grating spectral instruments has a specific problem: the superposition of
spectra of different order. De 1st order of  radiation has the same direction like 2nd
order of the /2 radiation.
4. Spectral lines have small bending.
5. They can work on any spectral range, if they are working by reflection on
metal surface.

Alb V1 R1 V2 V3 R2 R3

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

Fig. 3.4.

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LASERS OSPL Department – BUCHAREST UNIVERSITY OPTICS

Characteristics of gratings

di'
1. Angular Dispersion Du 
d

kn
Du 
cos 

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LASERS OSPL Department – BUCHAREST UNIVERSITY OPTICS

Characteristics of gratings

2. Power of Chromatic Resolution

The path difference for  + d is  = k( + d),

for  is  = k + /N

R = kN = knL

k – diffraction order,

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N – total number of grooves,
n – grooves density (gr/mm)
L – grating length (mm)

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LASERS OSPL Department – BUCHAREST UNIVERSITY OPTICS

Characteristics of grating instruments

3. Linear Dispersion is defined as for prism and will be:

dx fkn
Dl   f  Du 
d cos 
For small angles linear dispersion is nearly constant.

4. Brightness
Gratings blazed are used for a high brightness of desired order
spectrum (usually 1st). They have asymetric grooves.

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Fig. 3.5.

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LASERS OSPL Department – BUCHAREST UNIVERSITY OPTICS

Characteristics of grating instruments

(k+1)

k k()
Free spectral range

k(    (k + 1).

 = /k.

E.g. for diffraction order 100 free spectral range is only 1% of

observed radiation wavelength (at 5000 Å, Δλ = 50 Ǻ).

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LASERS OSPL Department – BUCHAREST UNIVERSITY OPTICS

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Resolvance of Grating

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LASERS OSPL Department – BUCHAREST UNIVERSITY OPTICS

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LASERS OSPL Department – BUCHAREST UNIVERSITY OPTICS

Examples of Resolvance

A standard benchmark for the resolvance of a grating or

other spectroscopic instrument is the resolution of the
sodium doublet. The two sodium "D-lines" are at 589.00
nm and 589.59 nm. Resolving them corresponds to
resolution power:

R = resolution power,

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dλ = resolution (or Δ λ).

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LASERS OSPL Department – BUCHAREST UNIVERSITY OPTICS

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LASERS OSPL Department – BUCHAREST UNIVERSITY OPTICS

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Non-imaging Imaging
(Magnification 1.6)

Input plane Output plane Input plane Output plane

200 mm 200 mm

400 mm 400 mm 640 mm

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LASERS OSPL Department – BUCHAREST UNIVERSITY OPTICS

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Quantum idea

based on

spectroscopic evidences!

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LASERS OSPL Department – BUCHAREST UNIVERSITY OPTICS

The quantum idea: Quantum mechanics was initially

developed to explain the atom,
Planck 1900
especially the spectra of light
Bohr 1913 emitted by different atomic
species. The quantum theory of
Schrodinger 1922
the atom developed as an
De Broglie 1924 explanation for the electron's
staying in its orbital, which could
Heisenberg 1932
not be explained by Newton's laws
Born of motion and by classical
electromagnetism.
Pauli

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LASERS OSPL Department – BUCHAREST UNIVERSITY OPTICS

SPECTROSCOPIC TIMELINE
Gen 1:3 "And God said 'Let there be light' "
Gen 9:13 "I set my bow in the clouds, and it shall be a sign ..."
4 C BC Aristotle recognizes that light was necessary for color to exist
AD 1300 first recorded use of lenses for eyeglasses
1600 Hans Lippershey makes first telescope after two children playing in his
shop put two lenses in front of each other
1609 Galileo produces telescope of power of 30x
1666 Newton observes spectrum obtained from a prism; 1687 publishes
Principia (Philosophiae Naturalis Principia Mathematica)
1678 Huygens proposed wave theory of light
1729 Pierre Bouguer notices attenuation of light as it passes through
successive thicknesses of glass

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1733 Joseph Priestly, father of chemistry in America, born
1735 Torbern Bergman born, father of qual and quant inorganic analysis

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LASERS OSPL Department – BUCHAREST UNIVERSITY OPTICS

What is light?
The general idea of the theory had been suggested by Robert
Hooke in 1664, but he had not investigated its consequences
in any detail.
Before modern times, only three ways had been suggested in
which light can be produced mechanically.
1. Either the eye may be supposed to send out something
which, so to speak, feels the object (as the Greeks believed);
2. or the object perceived may send out something which hits
or affects the eye (as assumed in the emission theory);
3. or there may be some medium between the eye and the
object, and the object may cause some change in the form

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or condition of this intervening medium and thus affect the
eye (as Hooke and Huygens supposed in their wave or
undulatory theory).

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LASERS OSPL Department – BUCHAREST UNIVERSITY OPTICS

SPECTROSCOPIC TIMELINE
1666 Newton observes spectrum obtained from a prism

The Opticks. The Opticks of 1704, which first appeared in English, is Newton's most
comprehensive and readily accessible work on light and color. In Newton's words, the
purpose of the Opticks was 'not to explain the Properties of Light by Hypotheses, but to
propose and prove them by Reason and Experiments.' Divided into three books, the
Opticks moves from definitions, axioms, propositions, and theorems to proof by
experiment. A subtle blend of mathematical reasoning and careful observation, the
Opticks became the model for experimental physics in the 18th century.

The Corpuscular Theory. But the Opticks contained more than experimental results.
During the 17th century it was widely held that light, like sound, consisted of a wave or
undulatory motion, and Newton's major critics in the field of optics--Robert Hooke and
Christiaan Huygens--were articulate spokesmen for this theory. But Newton disagreed.
Although his views evolved over time, Newton's theory of light was essentially
corpuscular, or particulate. In effect, since light (unlike sound) travels in straight lines
and casts a sharp shadow, Newton suggested that light was composed of discrete

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particles moving in straight lines in the manner of inertial bodies. Further, since
experiment had shown that the properties of the separate colors of light were constant
and unchanging, so too, Newton reasoned, was the stuff of light itself-- particles.

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 OSPL Department – BUCHAREST UNIVERSITY OPTICS

What is light?
LASERS

Newton said: “Rays of light are very small bodies emitted from shining
substances”
He probably said this because light travels (often) in straight lines (shadows).
He had great influence, but also his ideas of light described very well many of
the properties of light (operationally).
“Are not gross bodies and light convertible into one another; and
may not bodies receive much of their activity from the particles of light which
enter into their composition? The changing of bodies into light, and light into
bodies, is very conformable to the course of Nature, which seems delighted with
transmutations.”
“Truth is ever to be found in the simplicity, and not in the multiplicity
and confusion of things.”
He also realized that there must be some sort of ondulatory movement
involved with the interaction of light with matter. Usually, as we will see, the
colored fringes that we see looking at thin plates (Newton’s rings when one
surface is curved) are explained in terms of wave interference (and we will use
this model).
Another quote of Newton’s:
“As stones, by falling upon Water put the Water into an ondulatory
Motion and all Bodies by percussion excite vibrations in the Air; so the Rays of
Light, by impinging on any refracting or reflecting Surface, excite

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vibrations in the … Medium… and, by exciting them agitate the … Body; …
the vibrations thus excited are propagated in the … Medium … and move faster
than the Rays so as to overtake them”. (Newton – Optiks)

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 OSPL Department – BUCHAREST UNIVERSITY OPTICS

SPECTROSCOPIC TIMELINE
LASERS

1752 Thomas Melville writes of yellow light in flame when sea salt mixed with alcohol
1760 Johann Lambert gives mathematical formula to Bouguer
1776 Alessandro Volta notes different colors when using different sparking materials
1800 F.W. Herschel notes that different amounts of heat passed through different colored
glasses
(In 1800 William Herschel needed a colored filter for his telescope that would transmit a
maximum of light and a minimum of heat. For this purpose, he used a glass prism to
disperse sunlight into its components, and moved thermometers through the spectrum.
The temperature increased as the thermometers were moved from violet to red and
reached a maximum beyond the red end of the visible spectrum, Herschel referred to this
phenomenon as "invisible light“. )

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 OSPL Department – BUCHAREST UNIVERSITY OPTICS

SPECTROSCOPIC TIMELINE
LASERS

1800 Thomas Young demonstrates wave properties of light by diffraction

1801 J.W. Ritter discovers UV
1802 Thomas Young demonstrates wave nature of light by using a crude transmission
grating

1802 W.H. Wollaston observes dark lines in spectrum from prism (absorption)
1806 John Dalton proposes atomic theory. Daltonism explained.
1817 Josef Fraunhofer maps details of absorption lines in solar spectrum
1826 W.H.F. Talbot notices different salts yield different colored flames

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LASERS OSPL Department – BUCHAREST UNIVERSITY OPTICS

Absorption lines in the spectrum of the Sun, first studied and named by Joseph von
Fraunhofer in 1814. Altogether, Fraunhofer found some 700 lines in the solar spectrum.
The nine most prominent he labeled with capital letters A to K, starting at the red end. The
A and B bands are now known to be caused by absorption in Earth's atmosphere, while
the rest are due to absorption in the Sun's photosphere. C and F are now better known as
H-alpha and H-beta; the D lines are of sodium, the H and K lines of calcium, and the G
band by neutral iron and the CH molecule. All these features occur generally in stars of
spectral types F, G, and K.

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PLASMAS
LASERS OSPL Department – BUCHAREST UNIVERSITY OPTICS

Absorption lines in the spectrum of the Sun, first studied and named by Joseph von
Fraunhofer in 1814. Altogether, Fraunhofer found some 700 lines in the solar spectrum.
The nine most prominent he labeled with capital letters A to K, starting at the red end. The
A and B bands are now known to be caused by absorption in Earth's atmosphere, while
the rest are due to absorption in the Sun's photosphere. C and F are now better known as
H-alpha and H-beta; the D lines are of sodium, the H and K lines of calcium, and the G

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band by neutral iron and the CH molecule. All these features occur generally in stars of
spectral types F, G, and K.

PLASMAS
LASERS OSPL Department – BUCHAREST UNIVERSITY OPTICS

A Selection of Fraunhofer lines

Lines Due To Wavelengths (Å)

O2 (molecular oxygen in
A band 7594 - 7621
Earth's atmosphere)
O2 (molecular oxygen in
B band 6867 - 6884
Earth's atmosphere)

C (H-alpha) H (hydrogen) 6563

O2 (molecular oxygen in
a band 6276 - 6287
Earth's atmosphere)
D1 & D2 Na (sodium) 5896 & 5890
E Fe (iron) 5270
b1, b2, b3, b4 Mg (magnesium) 5184, 5173, 5169, 5167
c Fe (iron) 4958

F (H-beta) H (hydrogen) 4861

d Fe (iron) 4668
e Fe (iron) 4384

f H (hydrogen) 4340
G Fe 4308

SPECTROSCOPY
g Ca 4227
h (H-delta) H (hydrogen) 4102
H&K Ca (calcium) 3968 & 3934

PLASMAS
LASERS OSPL Department – BUCHAREST UNIVERSITY OPTICS

SPECTROSCOPIC TIMELINE
1838 W.A. Lampadius determines Fe and Ni in Co by comparing colors with standard
solutions
1850 J.J. Foucault measures speed of light in water
1852 August Beer shows logarithmic relation of Lambert

1852 G.G. Stokes used complementary filters to prove absorption at λ1 and emission at λ2
(nonresonance luminescence)
1852 E. Bequerel and J.W. Draper photograph solar spectrum
1852 Charles Wheatstone makes drawing of spark spectrum
1853 A. Muller & J. Duboscq use comparator for matching colors by adjusting solution
thicknesses
1859 G. Kirchhoff and R.W. Bunsen are the first to say that elements have both
characteristic absorption and emission spectra
1859 A.J. Angstrom measures ls in a flame and solar spectrum and compares the two

1868 J.N. Lockyer discovers Helium in solar spectrum and in 1873 describes "long" and

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"short" lines, the first quant work in spectroscopy
1882 H.A. Rowland shows that large concave reflection grating can be used for focusing &
dispersing
1885 J.J. Balmer develops empirical relationship for Hydrogen spectrum
PLASMAS
LASERS OSPL Department – BUCHAREST UNIVERSITY OPTICS

Hydrogen lamp

SPECTROSCOPY
PLASMAS
 OSPL Department – BUCHAREST UNIVERSITY OPTICS

Spectral series
LASERS

The most important discovery in regularity of atomic line spectrum was made by J.
Balmer (Swiss) in 1885. He discovered the line frequencies observed in visible range
of hydrogen atom
(λ = 656 nm, 486 nm, 434 nm & 410 nm)
are arranged by empiric formula:

 1 1 
ν ab  R 2  2 
2 n 
 
where νab is frequency of emission or absorption line, n = 3, 4 or 5; R is a constant
later called Rydberg’s constant. When the value of n increases the lines become
more frequent and go to a limit value of 365 nm (end of series).

SPECTROSCOPY
PLASMAS
LASERS OSPL Department – BUCHAREST UNIVERSITY OPTICS

SPECTROSCOPIC TIMELINE
1889 H. Ebert develops plane grating optical arrangement
1891 A.A. Michelson invents interferometer
1895 W.C. Roentgen discovers x-rays
1896 Zeeman sees splitting of lines in magnetic field

1900 A. Konig and F.F. Matens develop visible spectrometer

1900 Max Planck proposes quantum theory

1900 William Coblentz takes IR spectra of organics
1903 Mikhial Tswett separates plant pigments with adsorption chromatography
1905 Albert Einstein explains photoelectric effect

1909 Roberts, Pollack, and Leonard do photographic quant work

1911 E. Rutherford, H. Geiger, and E. Marsden discover nucleus of the atom
1913 Neils Bohr proposes "solar system" model of the atom

SPECTROSCOPY
1920 W.F. Meggers and P.D. Foote invent microphotometer
1923 A. Smekal publishes theoretical foundation of Raman spectroscopy
1924 Pauli postulates nuclear magnetic moments
PLASMAS
LASERS OSPL Department – BUCHAREST UNIVERSITY OPTICS

Also known as Zeeman splitting, the broadening or splitting of a spectral line into several
polarized components when the source is in a strong magnetic field; it is named after the
Dutch physicist Pieter Zeeman (1865-1943). Because the amount of Zeeman splitting and
of polarization depend on the magnetic field strength, this effect provides a power tool
for investigating cosmic magnetic fields. It was first used to map magnetic fields on the Sun,
especially in and around sunspots where the local field strength can be as high as 0.4 tesla
– thousands of times stronger than Earth's magnetic field. Across the Sun as a whole, and in

SPECTROSCOPY
the case of most other stars and cosmic objects, the field strengths are much lower and the
spectral lines are broadened rather than actually split by the Zeeman effect. However, weak
fields can still be studied by measuring the polarization of the line wings – the parts of a
spectral line well away from the central peak. Zeeman splitting is observed in the case of
some magnetic variables which are associated with intense magnetic fields.
PLASMAS
LASERS OSPL Department – BUCHAREST UNIVERSITY OPTICS

SPECTROSCOPIC TIMELINE

1926 W. Heisenberg and E. Schrodinger develop wave mechanics

1928 C.V. Raman sees nonresonant scattering
1929 Lundegardh is first to do quant work with flame photometer

1933 C.E. Gleeton and N.H. Williams perform first microwave absorption experiments
1935 Zablonski publishes energy level diagram for molecular luminescence
1938 H.M. Randall and F.A. Firestone use far IR for rotation spectroscopy
1940 Beckman Company begins marketing DU Quartz Spectrophotometer
1945 Felix Block and E.M. Purcell see emission and absorption, respectively, when
observing nuclear magnetic resonance
1949 W.D. Knight observes NMR chemical shifts
1949 Peter Fellgett performs Fourier transform of an interferrogram

SPECTROSCOPY
1949 John White and Max Listen develop double beam optical null IR spectrometer
1955 Alan Walsh develops atomic absorption spectroscopy

PLASMAS
LASERS OSPL Department – BUCHAREST UNIVERSITY OPTICS

SPECTROSCOPIC TIMELINE
1958 C. Townes, A.L. Schalow, and T.H. Maiman develop laser
1961 B.V. L'vov develops carbon rod furnace
1962 F.J. McClung and R.W. Hellwarth develop pulsed laser
1963 C. Th. J. Alkemade shows that fluorescence of metals can be stimulated in a flame
1964 J.D. Winefordner and T.J. Vickers develop atomic fluorescence spectroscopy
1964 Stanley Greenfield performs first ICP-AES
1966 P.P. Sorokin and J.R. Lankard develop dye laser

1968 R. Mavrodineau and R.C. Hughes publish several optical systems for multielement AA

1971 Intel Corp. introduces MCS-4 microprocessor

1972 Gary Horlick paper on use of Fourier transforms in spectroscopy using digital data
handling of spectra
1977 O'Haver, Harnly, and Zander develop 16 channel multielement AA
1978 M.P. Fuller and P.J. Griffiths develop diffuse reflectance FTIR

SPECTROSCOPY
1979 C.G. Enke and R.A. Yost develop triple quadrupole for MS-MS
1981 W. Slavin, D.C. Manning, and G.R. Carnick develop Stabilized Temperature Platform
Furnace
1983 S.B. Smith & G.M. Hieftje introduce pulsed hollow cathode background correction
PLASMAS
method for AA
 OSPL Department – BUCHAREST UNIVERSITY OPTICS

Spectral series
LASERS

The most important discovery in regularity of line spectrum of atoms was made by J.
Balmer (Swiss) in 1885. He discovered the line frequencies observed in visible range
of hydrogen atom
(λ = 656 nm, 486 nm, 434 nm and 410 nm)
are arranged by empiric formula:

 1 1 
ν ab  R 2  2 
2 n 
 
where νab is frequency of emission or absorption line, n = 3, 4 or 5. R is a constant
later called Rydberg’s constant. When the value of n increases the lines become
more frequent and go to a limit value of 365 nm (end of series).

SPECTROSCOPY
PLASMAS
 OSPL Department – BUCHAREST UNIVERSITY OPTICS

Spectral series
LASERS

In 1906 Theodore Lyman, who studied the emission spectrum of electrical

discharge in hydrogen, „saw” first line in ultraviolet (121,5 nm).

1 

SPECTROSCOPY
1
ν ab  R 2  2 
1 n 
 
PLASMAS
 OSPL Department – BUCHAREST UNIVERSITY OPTICS

Spectral series
LASERS

In 1908 was observed another line series emitted by

hydrogen atom in infrared range, called Paschen’s series.

n 4 5 6 7 8 9 10 11 12 13

Wavelength (nm) 1874.5 1281.4 1093.5 1004.6 954.3 922.6 901.2 886.0 874.8 866.2 820.1

Two lines due to hydrogen were observed by Paschen1 at the wave-

lengths 18,751 Å and 12,818 Å. According to the Bohr theory these are

SPECTROSCOPY
due to a electron falling into the third from the fourth and fifth stable
orbits in hydrogen atom.
1 Annalen der Physik, 27, 537, 1908
PLASMAS
LASERS OSPL Department – BUCHAREST UNIVERSITY OPTICS

A CLASSICAL VIEW OF
RADIATION
• James Clerk Maxwell is generally regarded as the greatest theoretical
physicist of the 19th century. Born in Edinburgh to a well-known Scottish family,
he entered the University of Edinburgh at age 15, around the time that he
discovered an original method for drawing a perfect oval. Maxwell was appointed
to his first professorship in 1856 at Aberdeen. This was the beginning of a career
during which he would develop the electromagnetic theory of light and
explanations of the nature of Saturn's rings, and contribute to the kinetic theory of
gases.
• Maxwell's development of the electromagnetic theory of light took many years
and began with the paper "On Faraday's Lines of Force," in which Maxwell
expanded upon Faraday's theory that the electric and magnetic effects result from
force fields surrounding conductors and magnets. His next publication, "On
Physical Lines of Force," includes a series of papers explaining the known effects
and the nature of electromagnetism.
• Maxwell's other important contributions to theoretical physics were made in the
area of the kinetic theory of gases. Here, he furthered the work of Rudolf Clausius,
who in 1858 had shown that a gas must consist of molecules in constant motion
colliding with one another and with the walls of the container. This resulted in
Maxwell's distribution of molecular speeds in addition to important applications of
the theory of viscosity, conduction of heat, and diffusion of gases.

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• Maxwell's successful interpretation of Faraday's concept of the electromagnetic
field resulted in the field equation bearing Maxwell's name. Formidable
mathematical ability combined with great insight enabled Maxwell to lead the way
in the study of the two most important areas of physics at his time. Maxwell died of
cancer before he was 50.

PLASMAS
LASERS OSPL Department – BUCHAREST UNIVERSITY OPTICS

At the age of 16, having just entered the University of

Munich, he was told by Philipp von Jolly, a professor
there, that the task of physics was more or less
complete (!). The main theories were in place, all the
great discoveries had been made, and only a few
minor details needed filling in here and there by
generations to come. It was a view, disastrously wrong
but widely held at the time, fueled by technological
triumphs and the seemingly all-pervasive power of
Newton's mechanics and Maxwell's electromagnetic Max Planck
theory. (1858-1947)

Planck later recalled why he persisted with physics: "The outside world
is something independent from man, something absolute, and the

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quest for the laws which apply to this absolute appeared to me as
the most sublime scientific pursuit in life."

PLASMAS
LASERS OSPL Department – BUCHAREST UNIVERSITY OPTICS

Blackbody radiation
While a student at Berlin from 1877 to 1878, Planck had been taught by Gustav Kirchhoff
who studied the spectra of light given off by hot substances. In 1859, Kirchhoff proved an
important theorem about ideal objects that he called blackbodies. A blackbody is something
that soaks up every scrap of energy that falls upon it and reflects nothing – hence its
name. It's a slightly confusing name, however, because a blackbody isn't just a perfect
absorber: it's a perfect emitter as well. In one form or another, a blackbody gives back out
every bit of energy that it takes in. If it's hot enough to give off visible light then it won't be
black at all. It might glow red, orange, or even white. Stars, for example, despite the obvious
fact that they're not black (unless they're black holes!), act very nearly as blackbodies; so,
too, do furnaces and kilns because of their small openings that allow radiation to escape only
after it's been absorbed and reemitted countless times by the interior walls. Kirchhoff proved
that the amount of energy a blackbody radiates from each square centimeter of its surface
hinges on just two factors: the frequency of the radiation and the temperature of the
blackbody. He challenged other physicists to figure out the exact nature of this dependency:
What formula accurately tells how much energy a blackbody emits at a given temperature
and frequency?

SPECTROSCOPY
PLASMAS
LASERS OSPL Department – BUCHAREST UNIVERSITY OPTICS

SPECTROSCOPY
PLASMAS
LASERS OSPL Department – BUCHAREST UNIVERSITY OPTICS

Planck's formula
Planck knew how the blackbody formula, first sought by Kirchhoff four decades
earlier, had to look mathematically at the high-frequency end of the spectrum
given that Wien's law seemed to work well in this region. And he knew, from the
experimental results, how a blackbody was supposed to behave in the low-
frequency regime. So, he took the step of putting these relationships together in
the simplest possible way. Between tea and supper, Planck had the formula in
his hands that told how the energy of blackbody radiation is related to
frequency. He announced his formula to the world at a meeting of the German
Physical Society on October 19, 1900.

SPECTROSCOPY
PLASMAS
LASERS OSPL Department – BUCHAREST UNIVERSITY OPTICS

Planck's law of black-body radiation

where
• is the amount of energy per unit surface per unit time per unit solid
angle emitted in the frequency range between ν and ν+dν;
• is the temperature of the black body;
• is Planck's constant;
• is the speed of light; and
• is Boltzmann's constant.

SPECTROSCOPY
PLASMAS
LASERS OSPL Department – BUCHAREST UNIVERSITY OPTICS

Energy quanta

To put a value on molecular disorder, Planck had to be able to add up the number of ways
a given amount of energy can be spread among a set of blackbody
oscillators; and it was at this juncture that he had his great insight. He brought in the
idea of what he called energy elements – little snippets of energy into which the total
energy of the blackbody had to be divided in order to make the formulation work. By late
1900, Planck had built his new radiation law from the ground up, having made the
extraordinary assumption that energy comes in tiny, indivisible lumps. In the paper he
wrote, presented to the German Physical Society on December 14, he talked about energy
"as made up of a completely determinate number of finite parts" and introduced a
new constant of nature, h, with the fantastically small value of about 6.6 × 10-27 erg
second. This constant, now known as Planck's constant, connects the size of a
particular energy element to the frequency of the oscillators associated with that
element.

For the first time, someone had hinted that energy isn't continuous. It can't, as every
scientist had blithely assumed up to that point, be traded in arbitrarily small amounts.

SPECTROSCOPY
Energy comes in indivisible bits. Planck had shown that energy, like matter, can't be
chopped up indefinitely. (The irony, of course, is that Planck still doubted the existence
of atoms!) It's always transacted in tiny parcels, or quanta. And so Planck began the
transformation of our view of nature and the birth of quantum theory.

PLASMAS
LASERS OSPL Department – BUCHAREST UNIVERSITY OPTICS

The Lorentz Oscillator Model

Lorentz thought of an atom as a mass
(the nucleus) connected to another
smaller mass (the electron) by a
spring.
The spring would be set into motion by an electric field interacting with
the charge of the electron. The field would either repel or attract the
electron which would result in either compressing or stretching the
spring. If Lorentz's system comes into contact with an electric field, then
the electron will simply be displaced from equilibrium. The oscillating
electric field of the electromagnetic wave will set the electron into
harmonic motion. Lorentz also considered the possibility of damping
in his model.
The system oscillates sinusoidally in time with some amplitude and phase shift relative to

SPECTROSCOPY
the electric field. This amplitude is a function of the frequency of the driving electric field. The
frequency that will maximize the amplitude is the resonant frequency.

PLASMAS
LASERS OSPL Department – BUCHAREST UNIVERSITY OPTICS

Plum pudding model (1906)

The plum pudding model of the atom was proposed by J. J. Thomson, the
discoverer of the electron in 1897. In this model, the atom is composed of
electrons, surrounded by a soup of positive charge to balance the electron's
negative charge, like plums surrounded by pudding. The electrons were thought
to be positioned throughout the atom, but with many electron structures possible,
particularly rotating rings. Instead of a soup, the atom was also sometimes said
to have had a cloud of positive charge. In Thomson's model, electrons were free
to rotate in rings which were further stabilized by interactions between the
electrons, and spectra were to be accounted for by energy differences of different
ring orbits. Thomson attempted to make his model account for some of the major

SPECTROSCOPY
spectral lines known for some elements, but was not notably successful at this.
(On the Structure of the Atom: an Investigation of the Stability and Periods of Oscillation of a number of
Corpuscles arranged at equal intervals around the Circumference of a Circle; with Application of the Results
to the Theory of Atomic Structure), published in the Philosophical Magazine

PLASMAS
LASERS OSPL Department – BUCHAREST UNIVERSITY OPTICS

Rutherford model (1911)

Rutherford came forth with his own model. In it,

the atom is made up of an Atomic nucleus
surrounded by a cloud of orbiting electrons.
Rutherford only commits himself to a region of
very high positive or negative charge in the atom,
but uses this language for pictorial purposes: "For
concreteness, consider the passage of a high
speed a particle through an atom having a
positive central charge N∙e, and surrounded by a
compensating charge of N electrons." However,

SPECTROSCOPY
the Rutherford model did not attribute any
structure to the orbits of the electrons.

PLASMAS
LASERS OSPL Department – BUCHAREST UNIVERSITY OPTICS

Niels Bohr ”On the Constitution of Atoms and Molecules",

Philosophical Magazine, Series 6, vol. 26, July 1913, pages 1-25.
The Hydrogen Atom

The inadequacy of the classical electrodynamics in accounting for the

properties of atoms an atom-model as Rutherford’s, will appear very
clearly if we consider a simple system consisting of positively
charged nucleus of very small dimensions and an electron
describing closed orbits around it. For simplicity, let us assume that the
mass of the electron is negligibly small in comparison with that of the
nucleus, and further, that the velocity of the electron is small compared
with that of light.
Now the essential point in Planck’s theory of radiation in that the energy
radiation from an atomic system does not take place in the continuos way
assumed in the ordinary electrodynamics, but that it, on the contrary, take

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place in distinctly separated emissions, the amount of energy
radiated out from an atomic vibrator of frequency n in a single
emission being equal to thn, where t is an entire number, and h is a
universal constant.
PLASMAS
LASERS OSPL Department – BUCHAREST UNIVERSITY OPTICS

We shall, for reasons referred to later, assume that the orbit in

question is circular; this assumption will, however, make no
alteration in the calculations for systems containing only a single
electron.

If is these expressions we give t different values, we get a series of

values for W and corresponding to a series of configurations of the
system.

SPECTROSCOPY
PLASMAS
LASERS OSPL Department – BUCHAREST UNIVERSITY OPTICS

(1) That the dynamical equilibrium of the systems in the stationary

states can be discussed by help of the ordinary mechanics states
cannot be treated on the basis.
(2) That the latter process is followed by the emission of a
homogeneous radiation, for which the relation between the frequency
and the amount of energy emitted is the one given by Planck’s
theory.

SPECTROSCOPY
PLASMAS
LASERS OSPL Department – BUCHAREST UNIVERSITY OPTICS

2
m  Ze  1 2
En   2   2
2  4 0  n

rn 
4 0  2
n 2

2
Ze m
2
m  e  2
 1 1
n ab  
3 

  2  2 

SPECTROSCOPY
4  4 0   na nb 
PLASMAS
LASERS OSPL Department – BUCHAREST UNIVERSITY OPTICS

2
~ m  e  2
R 
3 

  109737 cm 1

4  4 0 

Rexperimental = 109677,58 cm-1

“The agreement between the theoretical and observed values is

inside the uncertainty due to experimental errors in the
constants entering in the expression for the theoretical value.”

SPECTROSCOPY
PLASMAS
LASERS OSPL Department – BUCHAREST UNIVERSITY OPTICS

SPECTROSCOPY
PLASMAS
LASERS OSPL Department – BUCHAREST UNIVERSITY OPTICS

”We see that this expression accounts for the law connecting the
lines in the spectrum of hydrogen. If we put t2  2 and let t1 vary, we get
the ordinary Balmer series. If we put t2 = 3, we get the series in the
ultrared observed by Paschen and previously suspected by Ritz. If we
put t2 = 1 and t2 = 4, 5 we get series respectively in the extreme
ultraviolet and the extreme ultrared, which are not observed, but
the existence of which may be expected.
The agreement in question is quantitative as well as qualitative.”

SPECTROSCOPY
PLASMAS
LASERS OSPL Department – BUCHAREST UNIVERSITY OPTICS

SPECTROSCOPY
PLASMAS
LASERS OSPL Department – BUCHAREST UNIVERSITY OPTICS

SPECTROSCOPY
PLASMAS
LASERS OSPL Department – BUCHAREST UNIVERSITY OPTICS

“Spectra of other substances. In case of systems containing

more electrons we must -in conformity with the results of
experiments- expect more complicated laws for the line-spectra
than those considered. I shall try to show that the point of views
taken above allows, at any rate, a certain understanding of the laws
observed.”

SPECTROSCOPY
PLASMAS
LASERS OSPL Department – BUCHAREST UNIVERSITY OPTICS

Limits of planetary Bohr’s model :

- It cannot be applied to two or many electron atoms.
- Why only circular orbits?
- It is not possible to calculate the transition rate.

SPECTROSCOPY
PLASMAS
LASERS OSPL Department – BUCHAREST UNIVERSITY OPTICS

SPECTROSCOPY
PLASMAS
 OSPL Department – BUCHAREST UNIVERSITY OPTICS
Introduction to Stellar Spectra
LASERS

Study the spectrum of Vega, which shows the intensity of the light as a function of the
wavelength.

SPECTROSCOPY
PLASMAS
 OSPL Department – BUCHAREST UNIVERSITY OPTICS
Introduction to Stellar Spectra
LASERS

Study the spectrum of Star BD, which shows the intensity of the light as a function of the
wavelength.

SPECTROSCOPY
PLASMAS
LASERS OSPL Department – BUCHAREST UNIVERSITY OPTICS

Vector Model of Atomic Structure

A model of atomic structure in which spin and orbital angular momenta of
the electrons are represented by vectors.
1922 Magnetic dipolar momentum of atom (Stern-Gerlach) . Orbital
angular momentum is quantized

L  l
it's projection along a
direction of a magnetic
field:

Lz  m
has many values:

SPECTROSCOPY
m  l,  l  1,  l  2,..., l  1, l
It is called the magnetic quantum number because the application
of an external magnetic field causes a splitting of spectral lines
PLASMAS called the Zeeman effect.
LASERS OSPL Department – BUCHAREST UNIVERSITY OPTICS

Vector Model of Atomic Structure

1925 Electron Spin –intrinsic magnetic moment– (Zeeman effect)

Magnitude of spin s  ss  1

1 
s permitted 
2 values 2

SPECTROSCOPY
PLASMAS
LASERS
OSPL Department – BUCHAREST UNIVERSITY OPTICS

The movement of the electron around the nucleus and around axis is
characterized by 4 quantum numbers:
- n, principal quantum number;
- l, orbital quantum number;
- m, magnetic quantum number;
- s, spin quantum number.

n denotes the radial wave function and determines the energy of quantum
state.

l = 0, 1, 2, 3,...., n-1

SPECTROSCOPY
l = 0 circular orbits
l = 1 elliptical orbits

PLASMAS
LASERS OSPL Department – BUCHAREST UNIVERSITY OPTICS

The Atomic Orbitals for the Hydrogen Atom

En n l m Symbol for orbital

-K 1 0 0 1s
0 0
2 2s

2 1 1 2p+1 

2 0 2p0
1 px, py, pz
2 1 -1 2p-1 
3 0 0 3s
3 1 1 3p+1 

3 0 3p0
px, py, pz
1
3 1 -1 3p-1 
3 2 2 3d+2 

3 2 1 3d+1 |

SPECTROSCOPY

3 0 3d0
2

3 2 -1 3d-1 |
3 2 -2 3d-2 
PLASMAS
LASERS OSPL Department – BUCHAREST UNIVERSITY OPTICS

Visualizing the hydrogen electron orbitals

SPECTROSCOPY
Probability densities for the electron at different quantum numbers

PLASMAS
 OSPL Department – BUCHAREST UNIVERSITY OPTICS

n=1
LASERS

SPECTROSCOPY
PLASMAS
 OSPL Department – BUCHAREST UNIVERSITY OPTICS

n=2, l=0
LASERS

SPECTROSCOPY
PLASMAS
 OSPL Department – BUCHAREST UNIVERSITY OPTICS

n=2, l=1
LASERS

SPECTROSCOPY
PLASMAS
 OSPL Department – BUCHAREST UNIVERSITY OPTICS

n=3, l=0
LASERS

SPECTROSCOPY
PLASMAS
 OSPL Department – BUCHAREST UNIVERSITY OPTICS

n=3, l=1
LASERS

SPECTROSCOPY
PLASMAS
 OSPL Department – BUCHAREST UNIVERSITY OPTICS

n=3, l=2
LASERS

SPECTROSCOPY
PLASMAS
 OSPL Department – BUCHAREST UNIVERSITY OPTICS

n=4, l=0
LASERS

SPECTROSCOPY
PLASMAS
 OSPL Department – BUCHAREST UNIVERSITY OPTICS

n=4, l=2
LASERS

SPECTROSCOPY
PLASMAS
 OSPL Department – BUCHAREST UNIVERSITY OPTICS

n=4, l=3
LASERS

SPECTROSCOPY
PLASMAS
LASERS OSPL Department – BUCHAREST UNIVERSITY OPTICS

Hydrogen Atom

Selection Rules for

Electronic Transitions :
l  1
m  0,1
Allowed Transitions

These are the selection rules for an electric dipole transition.

The oscillating electric field associated with the transitions
resembles an oscillating electric dipole.

SPECTROSCOPY
PLASMAS
LASERS OSPL Department – BUCHAREST UNIVERSITY OPTICS

SPECTROSCOPY
PLASMAS
LASERS OSPL Department – BUCHAREST UNIVERSITY OPTICS

Zeeman Effect in Hydrogen

When an external magnetic field is applied, sharp spectral lines like
the n = 3→ 2 transition of hydrogen split into multiple closely spaced
lines. First observed by Pieter Zeeman, this splitting is attributed to
the interaction between the magnetic field and the magnetic
dipole moment associated with the orbital angular momentum. In the
absence of the magnetic field, the hydrogen energies depend only
upon the principal quantum number n, and the emissions occur at a
single wavelength.

SPECTROSCOPY
Normal Zeeman
effect (Lorentz triplet)
in strong magnetic
field
PLASMAS
LASERS OSPL Department – BUCHAREST UNIVERSITY OPTICS

Zeeman Effect in Hydrogen

π line, Δm = 0, polarized ║ with magnetic field,

visible transversal, is missing longitudinal

σ lines, Δm = ±1, circular polarized, ┼ on magnetic

SPECTROSCOPY
field, visible transversal and longitudinal

PLASMAS
 OSPL Department – BUCHAREST UNIVERSITY OPTICS
The Sodium Doublet
LASERS

The transition which gives rise to the doublet is from the

3p to the 3s level, levels which would be the same in the
hydrogen atom. The fact that the 3s ( l = 0) is lower than
the 3p (l = 1) is a good example of the dependence of
atomic energy levels on angular momentum. The 3s
electron penetrates the 1s shell more and is less
effectively shielded than the 3p electron, so the 3s level is
lower. The fact that there is a doublet shows the smaller
dependence of the atomic energy levels on the total
angular momentum . The 3p level is split into states with
total angular momentum j = 3/2 and j = 1/2 by the
magnetic energy of the electron spin in the presence of
the internal magnetic field caused by the orbital motion.
This effect is called the spin-orbit effect.
The magnitude of the spin-orbit interaction has the form
mzB = mBSzLz. In the case of the sodium doublet, the
difference in energy for the 3p3/2 and 3p1/2 comes from a
change of 1 unit in the spin orientation with the orbital part
presumed to be the same. The change in energy is of the
form
E = mBgB = 0.0021 eV

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where mB is the Bohr magneton and g is the electron spin
g-factor with value very close to 2. This gives an estimate
of the internal magnetic field needed to produce the
observed splitting:
m gB = (5.79 x 10-5 eV/T)2B = 0.0021 eV
PLASMAS B
LASERS OSPL Department – BUCHAREST UNIVERSITY OPTICS

Total Angular Momentum

When the orbital angular momentum and spin angular momentum are coupled,
the total angular momentum is of the general form for quantized angular
momentum

where the total angular momentum quantum number is

This gives a z-component of angular momentum

This kind of coupling gives an even number of angular momentum levels.

As long as external interactions are not extremely strong, the total angular

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momentum of an electron can be considered to be conserved and j is said to be
a "good quantum number". This quantum number is used to characterize the
splitting of atomic energy levels, such as the spin-orbit splitting which leads to
the sodium doublet.
PLASMAS
LASERS OSPL Department – BUCHAREST UNIVERSITY OPTICS

Spin-Orbit Interaction
The energy levels of atomic electrons are affected by the interaction
between the electron spin magnetic moment and the orbital angular
momentum of the electron. It can be visualized as a magnetic field
caused by the electron's orbital motion interacting with the spin
magnetic moment. This effective magnetic field can be expressed in
terms of the electron orbital angular momentum. The interaction
energy is that of a magnetic dipole in a magnetic field and takes the
form

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PLASMAS
 OSPL Department – BUCHAREST UNIVERSITY OPTICS
Hydrogen Fine Structure
LASERS

When the spectral lines of the hydrogen spectrum are examined at very high resolution, they are found to be
closely-spaced doublets. This splitting is called fine structure and was one of the first experimental evidences
for electron spin.

The small splitting of the spectral line is attributed

to an interaction between the electron spin S and
the orbital angular momentum L. It is called the
spin-orbit interaction.

The familiar red H-alpha line of hydrogen is a

single line according to the Bohr theory. The
straight application of the Schrodinger
equation to the hydrogen atom gives the same
result. If you calculate the wavelength of this
line using the energy expression from the Bohr
theory, you get 656.11 nm for hydrogen,
treating the nucleus as a fixed center. If you

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use the reduced mass, you get 656.47 nm for
hydrogen and 656.29 nm for deuterium. The
difference between the hydrogen and
deuterium lines is about 0.2

PLASMAS
LASERS OSPL Department – BUCHAREST UNIVERSITY OPTICS

Multi-electron Atoms

Helium
wavelengths (nm)
438.793 w
443.755 w
447.148 s
471.314 m
492.193 m
501.567 s
504.774 w
587.562 s
667.815 m

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s=strong,
m=med,
w=weak

PLASMAS
LASERS OSPL Department – BUCHAREST UNIVERSITY OPTICS

The Pauli Exclusion Principle

When they are in different orbitals (one or more of their n, l and

m values are different) then their spins may be paired or
unpaired. We could generalize these observations by stating
that "no two electrons in the same atom may have all four
quantum numbers the same." Stated in this way we see
immediately that any given orbital may hold no more than two
electrons. Since two electrons in the same orbital have the
same values of n, l and m, they can differ only through their spin
quantum number. However, the spin quantum number may
have only one of two possible values, and these possibilities are
given by (n, l, m, ↑) or (n, l, m, ↓).

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PLASMAS
LASERS OSPL Department – BUCHAREST UNIVERSITY OPTICS

Term Symbols
The heirarchy of labels for the electrons of multi-electron
atoms is configuration, term, level, and state.
The term uses the multiplicity 2S + 1, total orbital angular
momentum L, and total angular momentum J.
It assumes that:
- all the spins combine to produce S,
- all the orbital angular momenta couple to produce L,
- then the spin and orbital terms combine to produce a
total angular momentum J (Russel-Saunders coupling).
The angular momentum symbol follows the spectroscopic
notation scheme.
Different terms will in general have different energies, and
the order of those energies is usually that given by Hund's
Rules, although there are exceptions. The different terms

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for a given configuration are obtained by forming the
different combinations of angular momenta for the electrons
outside closed shells, making sure the Pauli Exclusion
Principle is obeyed.
PLASMAS
LASERS OSPL Department – BUCHAREST UNIVERSITY OPTICS

s = ½ , ↑ sau ↓ =>
S = 0, ↑↓ => spin multiplicity 2S+1=1, singlet state
or
S = 1, ↑↑ => spin multiplicity 2S+1=3, triplet state
One-electron atom has only singlet states.
2e atom has only singlet & triplet states.

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PLASMAS
LASERS OSPL Department – BUCHAREST UNIVERSITY OPTICS

Hund's Rules

1. The term with maximum

multiplicity lies lowest in energy

2. For a given multiplicity, the term

with the largest value of L lies
lowest in in energy.

3. For atoms with less than half-

filled shells, the level with the
lowest value of J lies lowest in
energy.

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Hund's rules assume combination
to form S and L, or imply L-S
(Russell-Saunders) coupling.
PLASMAS
LASERS OSPL Department – BUCHAREST UNIVERSITY OPTICS

Influences on Atomic Energy Levels

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PLASMAS
LASERS OSPL Department – BUCHAREST UNIVERSITY OPTICS

Helium Energy Levels

One electron is presumed

to be in the ground state,
the 1s state. An electron in
an upper state can have
spin antiparallel to the
ground state electron
(S=0, singlet state,
parahelium) or parallel to
the ground state electron
(S=1, triplet state,
orthohelium).

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PLASMAS
LASERS OSPL Department – BUCHAREST UNIVERSITY OPTICS

Selection Rules for Electronic Transitions :

l  1
Allowed Transitions m  0,1
j  0,1
S  0
Laporte rule: different parity,

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s↔p, p↔d
Notes:
These are the selection rules for an electric dipole transition.
All could be relaxed.
PLASMAS
LASERS OSPL Department – BUCHAREST UNIVERSITY OPTICS

The Solar Spectrum

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Explanation: Shown above are all the visible colors of the Sun. The above spectrum was
created at the McMath-Pierce Solar Observatory and shows, first off, that although our
yellow-appearing Sun emits light of nearly every color, it does indeed appear brightest in
yellow-green light. The dark patches in the above spectrum arise from gas at or above the
PLASMAS
Sun's surface absorbing sunlight emitted below. Since different types of gas absorb
different colors of light, it is possible to determine what gasses compose the Sun.
LASERS OSPL Department – BUCHAREST UNIVERSITY OPTICS

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PLASMAS