Atomic and Molecular Spectra

Atomic and molecular spectra
Atomic spectra
Hg
Ne
Emmision spectrum of iron
Emmision spectrum of hydrogen

Emission line & adsorption line
Atomic spectral lines are of two types:
An emission line is formed when an
electron makes a transition from a
particular discrete energy level of an atom,
to a lower energy state, emitting a photon
of a particular energy and wavelength. A
spectrum of many such photons will show an
emission spike at the wavelength
associated with these photons.
An absorption line is formed when an
electron makes a transition from a lower to
a higher discrete energy state, with a
photon being absorbed in the process.
These absorbed photons generally come
from background continuum radiation and a
spectrum will show a drop in the continuum
radiation at the wavelength associated with
Emission Absorption
the absorbed photons.
 If the energy of the atom or molecules is
confined to discrete values, for then energy can
be discarded or absorbed only in discrete
amounts
 If the energy of an atom decreases by E, the
energy is carried away as radiation of frequency
v  E / h
and a line appears in the spectrum
 The atomic and molecular spectra are
evidence for the quantization of
energy that observed from the
frequencies of radiation absorbed and
emitted by atoms and molecules.
 Emitted or absorbed radiation appear
at a series of discrete frequencies
Johann Balmer, 1885
 Pattern in the wavelengths or frequencies of
the lines in the atomic hydrogen spectrum
 Balmer showed that a plot of the frequency of
the lines versus 1/n2 is a linear plot
4
v  8.2202 x10 (1  2 ) Hz
14
n = 3,4,5,…..
Johann Balmer, 1885
Formula Balmer
Johann Balmer, 1885
A plot of frequency versus 1/n2 (n=3,4,5,…) for the

series of lines of the hydrogen atom spectrum that
occurs in the visible and near UV regions
Example:
Using Balmer’s formula, calculate the

wavelength of the first few lines of
the visible region of the hydrogen
atomic spectrum and compare them to
the experimental values
Solution:
The first line is obtained by setting n = 3, in
which the case we have
The next line is obtained by setting n=4, and so
Thus, we see that the agreement with the

experimental data
Balmer series
Emission spectrum of the hydrogen atom in

visible and the near UV region
The Rydberg formula account for all the lines in
the hydrogen atomic spectrum
All the lines in the hydrogen atomic spectrum

was accounted for by generalising the
Balmer formula
n1 dan n2 are integers but n2 is always greater

than n1
Rydberg formula
Rydberg constant (RH)
The first series of lines making up the
hydrogen atomic spectrum
Name n1 N2 Region of
electromagnetic
spectrum
Lyman 1 2,3,4… UV
Balmer 2 3,4,5… Visible
Paschen 3 4,5,6… Near IR
Bracket 4 5,6,7… IR
Pfund 5 6,7,8… Far IR
Question
Calculate the wavelength of the second

line in the Paschen series and show that
this lines lies in the near IR, that is , in
the IR region near the visible
Solution
1 1 1
v  109,680( 2  2 )cm
3 5
1
 7.799 x10 cm
3
  1.282 x10 cm  12,820 A

4
Angular momentum is a fundamental property
of rotating system
Energy kinetics of the revolving particle
Where v  2rvrot  rrot , whererot  2vrot

v
l  I  (mr )( )  mvr
2
r
Kinetic energy (in term of momentum)
mv 2 (mv) 2 p 2
K  
2 2m 2m
Kinetic energy (in term of rotating system)
I 2 ( I ) 2 l 2
K  
2 2I 2I
The correspondences between linear and rotating
systems
Type of motion
Linear Angular
Mass (m) Moment of inersia (I)
Speed (v) Angular speed
Momentum Angular momentum
Kinetic energy Rotational kinetic

energy
The rotation of a single particle
about a fixed point
Energy
Energy total = Energy kinetic + energy potential
Energy kinetics:
Energy total = Energy kinetic + energy potential
Bohr’s great contribution
Two non classical assumptions:

1. To assume the existence of stationary
electron orbits
2. Assumed that the angular momentum
of the electron must be quantized
4 o  2 n 2
r
me 2
n  1,2,...
Bohr ' sorbit are quantized
4 o  2 n 2
r
me 2
n  1,2,...
Bohr ' sorbit are quantized
me 4 1
En  
8 o 
2 2 2
n
n  1,2,....
The negative sign indicates that the energy states are
bound states
Energies are less than when the proton and electron are
infinitely separated
n=1 , the states of lowest energy (ground states energy)
me 4 1 1
E  2 2 ( 2  2 )  hv Bohr frequency condition
8 o h n1 n2
E  hv
me 4 1 1
v 2 3 ( 2  2)
8 o ch n1 n2
Rydberg’s constant
me 4
RH  2 3
8 o ch
Question
Calculate RH and compare the result to its

experimental value. 109,677 cm-1
m=9.10953x10-31kg
e = 1.602189x10-19C
h=6.626176x10-34Js
C=2.99792x108ms-1
= 8.85419x10-12C2N-1m-2
Question
 Calculate the ionization energy of the
hydrogen atom
Solution:
The ionization energy is the energy
required to take the electron from the
ground state to the first unbound state,
which is obtained by letting n2 =
unlimited

Atomic and Molecular Spectra

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Atomic and molecular spectra

Emmision spectrum of hydrogen

A plot of frequency versus 1/n2 (n=3,4,5,…) for the

Using Balmer’s formula, calculate the

Thus, we see that the agreement with the

Emission spectrum of the hydrogen atom in

All the lines in the hydrogen atomic spectrum

n1 dan n2 are integers but n2 is always greater

Calculate the wavelength of the second

  1.282 x10 cm  12,820 A

Energy kinetics of the revolving particle

Where v  2rvrot  rrot , whererot  2vrot

Kinetic energy (in term of rotating system)

Kinetic energy Rotational kinetic

Two non classical assumptions:

Calculate RH and compare the result to its

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