Chapter IV: Electronic Structure of Atom

To understand why pure substances have particular composition and

properties, we need to know about the electronic structure of atoms,
especially the way how are electrons arranged about the nucleus of atom
of different elements?
 Chapter IV: Electronic Structure of Atom
IV.1. Atomic model of Rutherford
Rutherford supposed that electrons move around the nucleus with sufficient
velocity to create a centripetal force equals to attraction force of nucleus.
But this atomic model had a limitation,
Because electrons revolve around the positively charged nucleus, it is not
possible for the long run as we know atoms are stable while any particles in
a circular orbit would undergo acceleration. During acceleration charged
particles would radiate energy. Revolving electrons will lose energy and
finally fall into the nucleus.
For solve this problem, scientists created a new theory called Energy
Quantification.
 Chapter IV: Electronic Structure of Atom
IV.2. Duality nature of light radiations
In our daily life we use energy like micro-wave for cooking, sunshine and
Wi-Fi, all of these examples looks different but they appeared the same
nature of electromagnetic radiation.
Scientists of light and physics were disagreed about the nature of light
radiation between wave and corpuscular behavior.
Many phenomena prove the wave nature of light without denying its
corpuscular behavior,
Finally it has been agreed in physics the possibility of adopting two
behaviors together.
 Chapter IV: Electronic Structure of Atom
IV.2.1. Wave nature of light
The light radiation is the propagation of two perpendicular fields: electrical
and magnetic fields, these previous are sinusoidal functions against time.
Light wave propagate in vacuum with velocity equals to : 3,108 m/s.
Each wave characterized by :
Frequency (υ)
Wavelength (λ)
Period (T)
Related by each other
  
 C =
T 
   C = 
T= 1 
  
 Chapter IV: Electronic Structure of Atom
The eyes of human being can detect a parte of wavelength (λ) scale called
visible range between 380 and 740 nanometer
 Chapter IV: Electronic Structure of Atom
IV.2.1. Corpuscular nature of light
The wave postulate of light cannot describe the discontinuity of energy and
other phenomena such as photoelectric effect, thus Max Planck and
Alfred Einstein proposed the theory of energy quantification:
✓ Planck showed that energy carried by light wave is a specific quantities
called Quantum equals to: E = h
 : is the light frequancy h: planck constant equals to 6,62  10-34 J / s

✓ Einstein showed that light radiation constituted of small particles called

photons transport energy equals to: E = m  C 2
m : the photon mass C: light velocity in vacuum
 Chapter IV: Electronic Structure of Atom
From two expressions we can detail

E = m  C2  m  C 2
C
  m  C 2
= h   = with  = and
E = h  h 
C m  C2 1 mC h
=  = =
 h  h mC
 Chapter IV: Electronic Structure of Atom
IV.2.1. Photoelectric effect
When a light beam (Eph=h.υ) impact the surface of a metal, a part of this
energy was used to remove electrons from the surface and the rest of energy
appear as kinetic energy (Ek) to transport the removed electrons towards
high levels
E ph = E 0 + E k
E 0 = h  0
1
Ek =  m  v2
2
E 0 : The necessary energy to remove electrons from the surface.
E k : The kenetic energy that transport electrons to high levels.
0 : limit frequancy of metal
 Chapter IV: Electronic Structure of Atom
E ph = E 0 + E k
1
 h   = h  0 +  m  v 2
2
1
 h  (  − 0 ) =  m  v 2
2
h  (  − 0 )
 v = 2
2

m
h  (  − 0 )
 v = 2
m
This is the expression of removed electron velocity
For photoelectrical effect must be : E ph  E 0 (   0 )
IV.3. Hydrogen emission spectrum
Using the electrical discharge in tube containing Hydrogen gas at low
pressure. A high potential was applied which excite hydrogen atoms to
produce red light.
When this light passes through a prism, it is dissociate into spectrum lines
on the photographic screen, each line of the spectrum represents
electromagnetic radiation with characteristic frequency. These lines called
Hydrogen Emission Spectrum.
1  1 1 
The wave number of each line expressed as follow :  = = R H  2 − 2 
  nf ni 
This expression called : Rydberg relationship of Hydrogen atom
RH: is the Rydberg constant equals to : RH = 1,1.107 m-1
ni and nf : are the first and the final levels which electron moves between.
 Chapter IV: Electronic Structure of Atom
❑ Hydrogen Emission Spectrum Interpretations
✓ When atom of Hydrogen exposed to radiations (other energy like
heating ) at low pressure that leads to exciting it, this excitation present
in the movement of electron from the first level (low energetic level) to
the final level (high energetic level )
✓ The moved electron doesn’t stay at the high levels but it returns to the
fundamental level (stable state) in one step or step by step between
levels, this retune is accompanied by spectrum emission.

Excitation Emission
 Chapter IV: Electronic Structure of Atom
❑ Hydrogen Emission Spectrum Interpretations
✓ There are five spectral series of transition each series named by its finder

 Lyman Serie : ni =1 ⎯⎯⎯

→ nf = 2, 3, 4, 5, 6, 7, ...... ( UV )
 Balmer Serie : ni =2 ⎯⎯⎯
→ nf = 3, 4, 5, 6, 7, ......... ( Vis )
 Paschen Serie: ni =3 ⎯⎯⎯
→ nf = 4, 5, 6, 7, .............. ( IR )
 Bracket Serie: ni =4 ⎯⎯⎯
→ nf = 5, 6, 7,................... ( IR )
 Pfund Serie : ni =5 ⎯⎯⎯
→ nf = 6, 7,....................... ( IR )
Chapter IV: Electronic Structure of Atom
IV.4. Hydrogen Absorption spectrum
For recognize the Hydrogen absorption spectrum we repeat the same
previous experiment but without prism, we observe black lines on the
photographic screen.
These black lines represent the Hydrogen spectrum of absorption.
✓ When an electron of hydrogen atom absorb light radiation (Energy
Quantity), it makes a transition from low level to high level.
✓ When an electron of hydrogen atom emit light radiation (Energy
Quantity), it makes a transition from high level to low levels.
The expression of this energy quantity as follow:

E = h   = E n f − E ni
IV.5. Bohr Model
Bohr assumed that atom is a small nucleus positively charged arounded by
electrons which move on orbitals with circular trajectory, this easy model
used as introduction to study Quantum mechanics.
This model named according to the scientist Niels Bohr who proposed it for
present Hydrogen atom, Bohr’s model matches with lines of emission
spectrum from Hydrogen atoms.
The model of Bohr study only mono-electronic atoms like : Hydrogen and
Hydrogenoïdes.
Hydrogenoïdes are ions that contain one electron such as Hydrogen but the
+ 2+ 3+ 4+
number of protons is different: 2 He , 3 Li , 4 Be , 5 B .
 Chapter IV: Electronic Structure of Atom
❑ examples of Hydrogenoïdes reactions
+ −
2 He ⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯
→ 2 He + e
2+ −
3 Li ⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯→ 3 Li + 2e
3+ −
4 Be ⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯
→ 4 Be + 3e
4+ −
5 B ⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯
⎯→ 5 B + 4e
 Chapter IV: Electronic Structure of Atom
IV.5.1. Bohr Postulates
✓ Electrons rotate on circular orbitals, each orbital has his own energy, in
this case atom doesn’t radiate. This orbitals called stable orbit.
✓ When an electron jump from orbital to an other, the difference of energy
h C
absorbed or emitted with one unite E = h   = = E nf − E ni

 Chapter IV: Electronic Structure of Atom
✓ momentum of movement quantity (Angular momentum m.v.r ) take only
 h 
values equals or multiple of  
 2 
h
m  v  r = n                        (1)
2
h
 v = n
2  m  r
n : is natural number ( n=1,2,3,4,5,...........)

IV.5.2. Calculating Bohr orbital radius

For Hydrogen and hydrogenoïdes according to Bohr model, the radius is the
distance between electron and nucleus.
 Chapter IV: Electronic Structure of Atom
Hydrogen atom ( 1 H ) and hydrogenoïdes ( Z X ( Z −1) +
) contain negative electron
and positive nucleus, thus create an attractive force (Fe) between them
defined by Column relationship

q1  q 2
Fe = K  2
r
q1 : charge of nucleus equals ( Z  e )  q 2 : charge of electron equals ( −e )
e2
Fe = −K  Z  2                   ( 2 )
r
K : is Column constant equals to 9  109 SI
 Chapter IV: Electronic Structure of Atom
Electron revolves in stable orbit and does not fall into nucleus because of an
other force called centripetal force (Fc) towards the opposite direction of
(Fe), v2
Fc = m  a n = m                   ( 3)
r
e2 v2
Fe = Fc  K  Z  2 = m 
r r
e2
 r = K Z                  ( 4)
mv 2

and from experssion (1) we can write

h
v = n                       ( 5)
2  m  r
we replace ( 5 ) in ( 4 )
K  Z  e 2  4 2  m 2
e2
r = K Z = r
 h 
2
n h
2 2

mn  
 2  m  r 
 n2  h2 
rn =  2                        ( 6)
 4  K  e  m 
2
Z
a0

n2
rn =  a0                      (7)
Z
O
−10
a 0 = 0,529  10 m = 0,53 A
From expression (7) we can calculate the orbital radius of Hydrogen and
hydrogenoïdes
 ()  ()
2 2
1 1 1
r1 =  a 0 = 0,53 Å r1 =  a 0 =  0,53 = 0, 265 Å
 1  2 2
 ( 2)
2  ( 2)
2

r2 = r2 = 4
 a 0 = 4  0,53 = 2,12 Å  a 0 =  0,53 = 1, 06 Å
 1 +  2 2
H  He 
( ) ( )
1 2 2 2
 3  3 9
3r =  a 0 = 9  0,53 = 4, 77 Å 3r =  a 0 =  0,53 = 2,38 Å
 1  2 2
 ( 4)  ( 4)
2 2
16
r4 =  a 0 = 16  0,53 = 8, 48 Å 4r =  a =  0,53 = 4, 24 Å
 
0
1 2 2
 Chapter IV: Electronic Structure of Atom
IV.5.3. Calculating orbital energy
The total energy of electron in its orbital equals to the sum of kinetic and
potential energies:
ET = E P + E K                      (8)

The potential energy EP equals to Column force when the electron with the
negative charge move from (r) to infinity ()
  
q1  q 2 e2
E P =  Fe  dr =  K  2  dr = −  K  Z  2  dr
r r r r r
K  Z  e2
EP = −                      (9)
r
 Chapter IV: Electronic Structure of Atom
The Kinetic energy EK can be expressed as follow:
1
EK =  m  v2
2
From expression (4)
e2
v = K Z
2

mr
We replace v2 in kinetic energy formula :

1  e2  K  Z  e2
EK =  m   K  Z  =                      (10 )
2  mr  2r

We replace kinetic and potential energies formula in the total energy formula

K  Z  e2 K  Z  e2 K  Z  e2  1 1 K  Z  e2
ET = − + =   −1 +  = − 
r 2r r  2 2 r
1 K  Z  e2
En = − 
2 rn
 By replacing radius (r) formula from expression (6) in the previous formula (En)
1 K  Z  e2 Z 2  22  K 2  e 4  m 
En = −  2 = 2 − 
2 n h 2
 n  h2 
  
 Z 4  2
 K  e 2
 m  E0

Z2
E n = 2  E 0                      (11)
n
 2 2  K 2  e 4  m  −19
E0 =  − 2  = − 21, 76  10 J = −13, 6 eV
 h 
 ()  ( )
2 2
1 2
E1 = 2  E 0 = E 0 = −13.6 eV E1 =  E 0 = 4  E 0 = −54.4 eV
(1) (1)
2
 
 
( )  E = E 0 = −13.6 = − 3,4 eV ( )
2

2
 1 2
E
 2 = E 2 =  E 0 = E 0 = −13.6 eV
( 2) ( 2)
2 0 2
 4 4
+ 
1H  2 He 
( 1) ( 2)
2 2
 E 0 −13.6  4 4
E
 3 =  E = = = − 1,5 eV E3 =  E 0 =  E 0 = −13.6  =-6,04 eV
( 3) ( 3)
2 0 2
9 9 9 9
 
 
( ) ( )
2 2
E = 1 E −13.6 E = 2 4 1
 E = 0
= = − 0,85 eV  E =  E = − 13.5  =-3,4 eV
 4 ( 4 )2 0 16 16  4
( 4)
2 0
16
0
4
 
 Chapter IV: Electronic Structure of Atom
IV.5.4. Calculating electron velocity on the orbital
From expression (1) we can write:
nh
vn =
2  m  rn
We replace ( rn ) from expression ( 6 ) in ( v n ) expression
nh Z  2  K  e 2 
vn = =  
n 2
h 2
 n  h 
2  m    2 
 Z 4   K  e 2
 m  v0

Z
v n =  v 0                       (12 )
n
2  K  e 2
v0 = = 2,18  106 m / s
h
This is the general formula to calculate the electron velocity on its orbital of
Hydrogen and Hydrogenoïdes
 Chapter IV: Electronic Structure of Atom
we can calculate the velocity of electron on each orbital for Hydrogen and
hydrogenoïdes

 Z 1  Z 2
 v1 =  v 0 =  2,18  10 6
= 2,18  10 6
m/s  v1 =  v 0 =  2,18  10 6
= 4,36  10 6
m/s
1 1 1 1
 
 v = Z  v = 1  2,18  106 = 1, 09  106 m/s  v = Z  v = 2  2,18  106 = 2,18  106 m/s
 2 2 0 2 + 
2
2
0
2
1 H  2 He 
Z 1
 v =  v =  2,18  106 = 0, 72  106 m/s  v = Z  v = 2  2,18  106 = 1, 45  106 m/s
 3 3 0 3  3 3 0 3
 Z 1  Z 2
 v 4 =  v 0 =  2,18  10 = 0,54  10 m/s
6 6
 v 4 =  v 0 =  2,18  106 = 1, 09  106 m/s
 4 4  4 4
IV.6. Relationship between energy and transition
From the energy relationship (En) for two levels (n1 and n2) we can write:
 Z 2  22  K 2  e 4  m  
E n1 = 2   − 2 
 n 1  h 
   E = E n 2 − E n1 = h  
 E = Z   − 2  K  e  m  
2 2 2 4

 n2 n 2  2 
 2  h 
 2 2  K 2  e 4  m  2  1 1  h C
E =    Z   2 − 2 
= h   =
 h 2
  1
n n 2  
1  2 2  K 2  e 4  m  2  1 1 
=   Z   2 − 2 
                      (13)
  h C
3
  n1 n 2 
RH

2 2  K 2  e 4  m
RH = = 1, 09738  10 7
m -1
 1,1  10 7
m -1

h3  C
Finally we can express the general formula od Rydberg
1  1 1 
= = R H  Z2   2 − 2                        (14 )
  n1 n 2 
IV.6. First and limit ray (line)
Each spectrum series characterized by two main rays the first ray and limit
ray
IV.6.1. Limit ray (infinity ray)
This ray produced when an electron move from (ni) to ( ) or the opposite,
it is characterized by the biggest wave-number:
1  1 1  1 R  Z 2
max = = R H  Z2   2 −    max = = H2
 min  ni    min ni

IV.6.2. First ray

This ray produced when an electron move from (n) to (n+1) or the opposite,
it is characterized by the smallest wave-number:
1  1 1 
min = = RH  Z   2 −
2

 max n ( n + 1)
2

 
IV.7. Ionization energy (Ei)
Ionization energy is the necessary energy for the electron transition from (n)
to ( ) expressed as follow:
Z2 Z2 Z2
Ei = ( E  − E n ) = 2  E 0 − 2  E 0 = − 2  E 0
 n n
e. g.:
Calculation of the ionization energy of Hydrogen from fundamental state:
Z2 Z2 Z2 12
E i ( 1 H ) = ( E  − E1 ) = 2  E 0 − 2  E 0 = − 2  E 0 = − 2  ( −13, 6 ) = +13, 6 eV
 1 1 1

Calculation of the ionization energy of Hydrogen from the 1st excited state:

Z2 Z2 Z2 12
E i ( 1 H ) = ( E  − E 2 ) = 2  E 0 − 2  E 0 = − 2  E 0 = − 2  ( −13, 6 ) = +3, 4 eV
 2 2 2
Calculation of the ionization energy of (2He+) from fundamental state:
Z2 Z2 Z2 22
E i ( 2 He ) = ( E  − E1 ) = 2  E 0 − 2  E 0 = − 2  E 0 = − 2  ( −13, 6 ) = +54, 4 eV
+

 1 1 1
 Chapter IV: Electronic Structure of Atom
IV.8. Sommerfeld Model
The atomic model of Sommerfeld is an extension and development of Bohr
Model that proposed formulas which explain electron energies on each
energetic level then he applied all formulas on Hydrogen and
Hydrogenoïdes atoms.
Bohr's biggest contribution in his model was to introduce quantum
principles to classical physics, but his model had a few limitations:
✓ Spectra of Large atoms: The Bohr model could only successfully
explain the hydrogen spectrum. It could not accurately calculate the
spectral lines of larger atoms. The model only worked for
Hydrogenoïdes atoms, if the atom had only one electron.
 Chapter IV: Electronic Structure of Atom
✓ Relative Spectra Intensity: Bohr's model could not explain why the
intensity of the spectra lines were not all equal.
✓ Hyperfine spectral lines: with better equipment and careful observation,
it was found that there are previously undiscovered spectral lines. These
were named hyperfine lines and they accompanied the other more visible
lines. Bohr's model could not explain why this was the case due to the
lack of equipment and development in quantum physics
✓ The Zeeman Effect: It was found that, when hydrogen gas was excited
in a magnetic field, the produced emission spectrum was split. Bohr's
model could not account for this. Solved by accounting for the existence
of a tiny magnetic moment of each electron.
Sommerfeld model explains the fine spectrum of Hydrogen atom. The
important postulates of Sommerfeld atomic model are
✓ The orbits may be both circular and elliptical
✓ When path is elliptical, then there are two axis – major axis and minor
axis. When length of major and minor axis becomes equal then orbit is
circular.
 Chapter IV: Electronic Structure of Atom
h
✓ The angular momentum of electron moving in an elliptical orbit is ( n  ).
2
b
Where n is an integer except zero. Value of n = 1,2,3,4….. and ( ) = length
a
of major axis / length of minor axis. With increase in value of n, ellipticity of
the orbit decreases. When b = a, then orbit is circular.

✓ Sommerfeld suggested that orbits are made up of sub energy levels. These are
s, p, d, f. These sub shells possess slightly different energies.
Sommerfeld introduced a new quantum number called Orbital or Azimuthal
Quantum number ( l ) which determines the orbital angular momentum of
electron.
 Chapter IV: Electronic Structure of Atom
IV.9. Quantum numbers
IV.9.1. Principal quantum number (n)
Electrons are distributed on stable orbits called electronic layers (levels),
they are symbolized by Latin letters (K, L, M, N, O, P and Q) or by
numbers, each layer correspond an energetic level determined by the
principal quantum number n
n = 1 ⎯⎯⎯⎯⎯
→K

n = 2 ⎯⎯⎯⎯⎯→L

n = 3 ⎯⎯⎯⎯⎯→M
n = 4 ⎯⎯⎯⎯⎯→N

n = 5 ⎯⎯⎯⎯⎯→O

IV.9.2. Angular momentum quantum number (l)
This number represents the deflection of elliptical path from the circular
trajectory of electron, this theory prove the ellipticity of orbits, and circular
orbit is a specific case of this theory in which major axis and minor axis
were equal (a = b).
n2
a = rn =  a0
Z
b +1
=
a n
b +1
0  1 0   1  0  + 1  n  −1  + 1  n − 1
a n
: is a natural number
so 0  + 1  n − 1

The maximal value of angular momentum quantum number is 3

0  +1  3
e. g.:
K ⎯⎯⎯⎯⎯→n =1  =0

L ⎯⎯⎯⎯⎯→n = 2  = 0, 1

M ⎯⎯⎯⎯⎯ →n = 3  = 0, 1, 2
 N ⎯⎯⎯⎯⎯
→n = 4  = 0, 1, 2, 3

O ⎯⎯⎯⎯⎯→n = 5  = 0, 1, 2, 3

The maximal value of angular momentum quantum number represent the
Under-layer (s, p, d, f)
n = 1 ⎯⎯⎯⎯⎯
→ = 0  under-layer 1S

n = 2 ⎯⎯⎯⎯⎯→ = 0, 1  under-layers 2S , 2P

n = 3 ⎯⎯⎯⎯⎯→ = 0, 1, 2  under-layers 3S , 3P, 3d
n = 4 ⎯⎯⎯⎯⎯→ = 0, 1, 2, 3  under-layers 4S , 4P, 4d, 4f

 Chapter IV: Electronic Structure of Atom
IV.9.3. Magnetic quantum number (m)
This quantum number represents number of Quantum Boxes in the
electronic under-layer.
− m+
e. g.:

 n = 1 ⎯⎯⎯⎯⎯→ = 0  m = 0 ( one Quantic box )


 n = 2 ⎯⎯⎯⎯⎯  =0m=0
→ = 0, 1  
  = 1  m = −1, 0, + 1

  =0m=0
 n = 3 ⎯⎯⎯⎯⎯ 
→ = 0, 1, 2   = 1  m = −1, 0, + 1

  = 2  m = −2, −1, 0, + 1, +2

 Chapter IV: Electronic Structure of Atom
IV.9.4. Spin quantum number (s)
The spinal quantum number define the type of rotation (motion) around its
spin axis, may be in the direction of clockwise or counter-clockwise, this
number can take two values

 1
s = + 2 spin towards the upwards






 1
s=− spin towards the downwards
 2