The Atomic Spectra

1. Continuous Spectrum

2. Emission Line Spectrum

3. Absorption Line Spectrum

Dr. Sabry El-Taher 1

 1. Continuous Spectrum
A luminous solid or liquid, or sufficiently dense gas, emits
light of all wavelengths (colors) and produces a continuous
spectrum.

Dr. Sabry El-Taher 2

2. Emission line spectrum

A low-density, hot gas emits light whose spectrum consists

of a series of discrete bright emission lines. These lines are
characteristic of the chemical composition of the gas. Each
line has a different wavelength and color.

Dr. Sabry El-Taher 3

Examples of Emission Line Spectra

The line emission

spectrum of an
element is a
“fingerprint” for
that element, and
can be used to
identify the
element!

Line spectra are a

problem; they
can’t be explained
using classical
physics …

Dr. Sabry El-Taher 4

 3. Absorption line spectrum

A cool gas absorbs certain wavelengths from a

continuous spectrum, leaving dark absorption lines in
their place. These lines are also characteristic of the
chemical composition of the gas.

Dr. Sabry El-Taher 5

Emission and Absorption Spectra of Na

Dr. Sabry El-Taher 6

Emission Spectrum of Hydrogen
1. The Balmer Formula (1885)

Joseph Balmer first noticed that the frequency of visible lines in

the H atom spectrum could be reproduced by:

Where n is an integer, n = 3, 4, 5 …

• This equation accounted only for

lines in the visible and near u.v.

• The above equation predicts that

as n increases, the frequencies
become more closely spaced.

Dr. Sabry El-Taher 7

Dr. Sabry El-Taher 8
 2. The Rydberg Formula (1890)

Rydberg generalized the Balmer’s formula to account for all the lines
of the hydrogen atomic spectrum outside the visible region

where both n1 and n2 are integers but n2 is always greater than n1

The modern value of the Rydberg constant, RH, is 109677.57 cm-1.

 The line atomic spectra couldn’t be explained by classical physics.

Dr. Sabry El-Taher 9
Dr. Sabry El-Taher 10
The Bohr Model of Hydrogen Atom
Classical physics predicts that an electron revolving around a
nucleus will lose energy and spiral into the nucleus, and so a
stable orbit is classically forbidden.
Bohr’s general assumptions:
Niels Bohr (1885 – 1962)
Stationary states, exist in atoms and have
well-defined energies, En. in which orbiting n=2 n=1
electrons do not radiate energy, Transitions
can occur between them, yielding light of
energy:
E = En − En’ = hn
The angular momentum of the nth state is
quantized: L = mvr = nħ where n is called the n=3
Principal Quantum Number (ħ = h/2)
Dr. Sabry El-Taher 11
Bohr Radius
The angular momentum is: L  mvr  n
So the velocity is: v  n / mr
e 2
mv 2
n2 2
e 2
4 0 2

But  So   r  a0
4  r 2
r
2 2
m r 4 0 mr me 2

4 0 2

Solving for rn rn  n 2 a0 where a0 

me 2
a0 is called the Bohr radius. It is equal to:

The “ground” state Hydrogen atom diameter is:

Dr. Sabry El-Taher 12
The Hydrogen Atom Energies
The classical result for the energy:

1 e 2
1  e 2
  e 2

E  mv 
2
   
2 4 0 r 2  4  r   4  r 
e2 4 0 n 2 2
En   since rn 
8 0 rn me 2
So the energies of the stationary states are:

or: En =  E0/n2
Where E0 = 13.6 eV.
Dr. Sabry El-Taher 13
Transitions in the Hydrogen Atom
Bohr model is capable of reproducing the energy levels given by the
empirical formulas of Balmer and Rydberg.

18 Z 2
E  2.178x 10 J 2
n 

E photon  E  EU  E L

nU EU

nL EL

E ph E  1 1 
n   109 , 800  2  2  cm -1
hc hc  nU n L 

Close to RH = 108,680 cm-1

Dr. Sabry El-Taher 14
The Bohr Model (cont.)
Example: At what wavelength will emission from
n = 4 to n = 1 for the H atom be observed?

18  1 1 
E  2.178x 10  2  2  Joules
 nU n L 
1 4
18  1 18
E  2.178x 10  1     2 .04 x 10 J
 16 

hc
E  2.04x 10 18
J    9.74x 108 m  97.4nm


Dr. Sabry El-Taher 15

The Bohr Model (cont.)
Example: What is the longest wavelength of light that will result in
removal of the e- from H?

18  1 1 
E  2.178x10 J 2  2 
 nU nL 
 1

E  2.178x1018 J  0  1  2.178x1018 J

hc
E  2.178x10 18
J   9.13x108 m  91.3nm


Dr. Sabry El-Taher 16

Extension to Higher Z
The Bohr model can be extended to any single electron system
must keep track of Z (atomic number).
Examples: He+ (Z = 2), Li+2 (Z = 3), etc.
Example: At what wavelength will emission from n = 4 to n = 1 for
the He+ atom be observed?
 1 1 
E  2.178x10 18
J Z 2
  2  2
 nU nL 
2
1 4
 1
E  2.178x10 J  4   1    8.16x10 18 J
18

 16   H   He
hc
E  8.16x10 18
J   2.43x108 m  24.3nm

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Successes of the Bohr Theory
 The Bohr model was a great step in the new quantum theory,
It had made three important postulates:
1) electrons exist only in discrete energy levels, and
2) Energy is absorbed as photons to excite the electron
from one level to a higher energy level, and is emitted as
photons in dropping to a lower energy level.
3) The angular momentum is quantized (L = mvr = nħ ).

 Explained several features of the hydrogen spectrum

 Predicts a value for RH that agrees with the experimental value.
 Gives an expression for the radius of the atom.
 Predicts energy levels of hydrogen atom.
 Gives a model of what the atom looks like and how it behaves.
 Can be extended to “hydrogen-like” atom (those with one
electron, e.g. He+1, Li+2)
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 Limitations of the Bohr Model

1) Works only for single-electron (“hydrogenic”) atoms.

2) Could not account for the intensities or the fine structure
of the spectral lines (for example, in magnetic fields).
3) Could not explain the binding of atoms into molecules.
4) It was a one-dimensional model (radius) that used one
quantum number n to describe the distribution of electrons
in a 3D- atom.

Dr. Sabry El-Taher 22

 Louis V. de Broglie(1892-1987)
Wavelike Properties of Matter
if light can display wave-particle duality, then matter might
also display wavelike properties under certain conditions.

Louis de Broglie’s hypothesis stated that an object in

motion behaves as both particle and wave, just as light
does.
Einstein had shown from relativity theory that the wavelength, , and
the momentum, p, of a photon are related by
h

p
De Broglie argued that both light and matter obey this equation. Because
the momentum of a particle is given by mv, this equation predicts that a
particle of mass m moving with a velocity v will have a de Broglie
wavelength given by
h

mv
Dr. Sabry El-Taher 23
 The de Broglie wavelength of the baseball is so small to be
detectable. The reason is the large value of m.
Dr. Sabry El-Taher 24
 The wavelength of the electron corresponds to the wavelength of X
rays. It predicts that electrons can be observed to act like X rays.

Dr. Sabry El-Taher 25

The de Broglie Waves in Hydrogen Atom
de Broglie's hypothesis can be used to give a simple,
physical argument for the quantized Bohr orbits.
According to Bohr’s assumptions
nh
mvr = =n
2π
de Broglie assumed that the electron orbit would be allowed only if it
contained an integral number of electron wavelengths. Because the
circumference of a circle is 2r , we have the quantum condition

h
2r  n  n
p
Multiplying by p/2, we find the angular momentum:

nh
rp = = nh = mvr
2π
Dr. Sabry El-Taher 26
 The equation mvr = nħ can be used to calculate the velocity of an
electron in a Bohr orbit.

Dr. Sabry El-Taher 27

de Broglie Waves: Experimental Evidences
X-ray Diffraction Patterns
When a beam of X-rays is directed at a crystalline substance, the beam
is scattered in a definite manner characteristic of the atomic structure of
the crystalline substance. This phenomenon is called X-ray diffraction
and occurs because the interatomic spacings in the crystal are about
the same as the wavelength of the X-rays.

The similarity of the two patterns

shows that electrons behave like
X-rays and display wavelike
properties.

The wavelike property of electrons

is used in electron microscopes.
X-ray Diffraction Electron Diffraction

Dr. Sabry El-Taher 28

de Broglie Waves: Experimental Evidences
The Double-Slit Experiment
One of the principal experiments that
displays the wave properties of light is the
interference of two beams of light. The first
experiment showing interference of light
was performed by Thomas Young (1807)

In 1961, C. Jönsson, Germany,

succeeded in showing double-slit interference
effects for electrons by constructing very
narrow slits and using relatively large distances
between the slits and the observation screen.

Electron Double-Slit Experiment

Dr. Sabry El-Taher 29
de Broglie Waves: Experimental Evidences
 In 1927, Davisson and Germer:
Experimentally confirmed de Broglie’s
hypothesis by reflecting electrons from a
Ni crystal surface and observing
diffraction effects.
Diffraction of monoenergetic beams of
electrons by metal crystals, much like
the diffraction of x-rays. measurements
showed that de Broglie's formula gives
the correct wavelength.

 1932, Stern observed diffraction effects

with He atoms and H2 molecules, verifying
that the wave effects are not peculiar to
electrons, but for all microscopic particles.

Dr. Sabry El-Taher 30

Heisenberg’s Uncertainty Principle
It is impossible to specify both the position and the
momentum of a particle simultaneously with unlimited
precision.
Werner Heisenberg (1901-1976)

To locate the electron accurately within a region of x, we must use

light with x. Some of the photon's momentum must be transferred
to the electron in the process of locating it, causing change in the
momentum of the electron.

if we wish to locate an electron to within a region x, there will be an

uncertainty in the momentum of the electron. Heisenberg was able to
show that if p is the uncertainty in the momentum of the electron, then

ΔxΔpx  h

Dr. Sabry El-Taher 31

Dr. Sabry El-Taher 32
Although the Heisenberg uncertainty principle is of no consequence for everyday
macroscopic bodies, it has very important consequences in dealing with atomic
and subatomic particles.

Dr. Sabry El-Taher 33