ATOMIC STRUCTURE

PROFESSOR ZAHID IQBAL CHEEMA

Higher Education Department (HEC)
Contact No: 03334493343, 03356771333
Electromagnetic Radiations
• Don’t require any medium to travel in space.
• Travel with the velocity of light.
• Consist of electric and magnetic field that oscillate in direction perpendicular to
each other and direction in which they are travelling.
Characteristics of Electromagnetic Radiations
Wavelength
Distance between two nearest crests or nearest troughs. Measured in m,
cm , nm or A.

Frequency
Number of waves which pass through one point in one second.
c = v𝞴
Measured in Hertz or cycle per second.

Wavenumber & Velocity

• Distance covered by wave in one second termed as velocity.
• Reciprocal of wavelength or number of wavelengths per cm termed
as wavenumber.
Planck’s Quantum Theory

• Radiant energy is emitted discontinuously in the

form of energy packets or quanta.
• Energy associated with each quantum is directly
related to frequency of radiation.
• E∝υ
-34
• E = h υ where; h = 6.626 × 10 Js
• Energy associated with all quanta is given by:
• E = n h υ where; n = number of quanta
• A quantum in case of light is called a photon.
 Thomson’s Model of Atom (Plum-Pudding Model)
• The positive charge of the atom is like a sphere in which negatively charged
electrons are embedded.
Rutherford 𝞪-Scattering Experiment
• The beam of particles was bombarded on thin foil of gold (0.0004 cm thick),
across the foil a screen of Zn S was kept.

Observations
• Most of the 𝞪-particles were undeflected through gold foil.
• Only some of them got deflected by large angles.
• About 1 in 20,000 𝞪-particles reflected back.

Ruther ford Model

 CONCLUSIONS
• Most of the atom is empty. So the 𝞪-particles go across undeflected.
• The positive charge is concentrated in a very small space in an atom, which
deflected the positively charged 𝞪-particles.
• This small and heavy positively charged center is called nucleus.
• 𝞪-particles that happen to travel in line with the nucleus get deflected by 180˚.
RUTHERFORD’S MODEL
• An atom consists of heavy positively charged center called nucleus where most of the mass of atom is
concentrated. Protons and neutrons are present in the nucleus.
• Size of nucleus is very small as compared to the size of atom.
• Around nucleus, there is extra nuclear part where electrons are present.
• Electrons revolve around the nucleus in circular orbits like planets around the sun called planetary
electrons.
 DEFECTS OF RUTHERFORD MODEL
• Electron should lose energy continuously.
• It should move closer and closer to the nucleus due to the loss of energy and
ultimately should spiral down into the nucleus. So, atom should collapse. But
atom is stable itself. Also the observed spectrum of the atom is not continuous.
BOHR’s MODEL OF AN ATOM
• An atom has nucleus which is positively charged contains protons and neutrons.
• Negatively charged electrons moving around the nucleus in circular orbits.
• An electron cannot revolve anywhere but it can revolve around the nucleus in
certain permitted orbits where angular momentum of electron is equal to
𝑛ℎ
𝑞𝑢𝑎𝑛𝑡𝑖𝑧𝑒𝑑 .
2𝜋
CONTINUE……….
2ℎ
𝑚𝑣𝑟 =
2𝜋
Where, n = 1, 2, 3, …….. r = radius of the orbit h = plank’s constant
• In each stationary orbit electron has definite amount of energy and said to be in
ground state.
• Energy of electron goes on increasing while moving away from the nucleus.
• An electron in ground state can absorb certain amount of energy and get shifted to
excited state.
• In the exited state, electron is unstable emits the absorbed energy which is equal
to the difference in energy of two orbits.
• Force of attraction between nucleus and electron is equal to the centrifugal force
of electron.
 Velocity of the Electron Radius of the orbit Energy of the Electron

𝒛
v∝ 𝒏𝟐
En =
−𝟐𝝅𝟐 𝒏ⅇ𝟒 𝒛𝟐
𝒏 r∝ 𝒏𝟐 𝒉𝟐
𝒛

𝒗𝟏 𝒛𝟏 𝒏𝟏
= × 𝒓𝟏 𝒏𝟐𝟏 𝒛𝟐 −𝒛𝟐
𝒗𝟐 𝒛𝟐 𝒏𝟐 = × En ∞ 𝒏𝟐
𝒓𝟐 𝒏𝟐𝟐 𝒛𝟏

𝒏𝟐 𝑬𝟏 𝒛𝟐𝟏 𝒏𝟐𝟐
v = 2.188 × 𝟏𝟎𝟔 𝒎𝒔−𝟏 r = 0.529 × 𝑨𝒐 = =
𝒛 𝑬𝟐 𝒛𝟐𝟐 𝒏𝟐𝟏

Value of En in different Units: 𝑧2 -1

• −13 ⋅ 6
𝑛2
eV atom

𝑧2 -1
• −1312
𝑛 2 kJ mol

𝑧2
-1
• −21.79 × 10−19 2
𝑛
J atom
𝑧2 -1
• −313.6
𝑛2
K cal mol
Relation Between Kinetic Energy, Potential Energy, and Total Energy of the Electron

1 1
In C. G. S. KE = 𝑚𝑣 2 P. E = −𝑚𝑣 2 TE = − 𝑚𝑣 2
2 2

Orbital Frequency Time Period of Electron

The number of revolutions per second −16
𝑧2
1.5 × 10
𝑧2 𝑛3
15
6.66 × 10 𝑝𝑒𝑟 𝑠𝑒𝑐𝑜𝑛𝑑
𝑛3
Different Modes of Transition Between Two Orbits
n3
Δ𝐸1 = Δ𝐸2 + Δ𝐸3 ∆E2

𝑣1 = 𝑣2 + 𝑣3 n2
∆E3
1 1 1
= +
𝜆1 𝜆2 𝜆3
n1
 Rydberg Equation
Total Number of Spectral Lines for Transition

If the electron jumps from n2 to n1 1 1 1 2

𝑣ҧ = = 𝑅 2 − 2 𝑧
𝜆 𝑛1 𝑛2
Number of lines = ∑ ( n2 – n1) where n2 > n1 are the number of orbits
An example is transition from 6th orbit to 2nd Z = atomic number
R = Rydberg constant = 109678 cm-1
Number of lines = ∑ ( 6 – 2) 𝑣ҧ = wavenumber and 𝞴 = wavelength
∑ 4 = 4 + 3 + 2 +2 +1 = 10
1 2𝛱2 𝑚ⅇ4 1 −1 2
𝑣ҧ = = 2 2 𝑧
𝜆 ℎ3 𝐶 𝑛1 𝑛2
Reduced Mass and Modification in Rydberg Equation

• Whenever a particle moves in a circle around another particle of finite mass, the other particle must also
move in a circle around the common center of mass. Therefore, the motion of the nucleus must be taken
into account.
• In such cases the motion of one body may be neglected is the mass of the other body is replaced by reduced
mass. Reduced mass is calculated as follows in this case.
1 1 1 𝑀𝑚
= 𝑀 + 𝑚 𝑜𝑟𝜇 = 𝑀+𝑚 M = mass of nucleus, m = mass of electron
𝜇

Now, Rydberg equation becomes; 𝟏 𝟏

ഥ=𝑹 𝟐− 𝟐
𝒗
𝝒 𝒚
1 2𝛱 2 𝜇𝑒 4 1 −1
𝑣ҧ = = 𝑧2
𝜆 ℎ3 𝐶 𝑛12 𝑛22
(Ritz Combination Principle)
 Hydrogen Spectrum

All the spectral lines of hydrogen can be grouped into the following:

Name of the Series Spectral Region n1 n2

Lyman Series Ultraviolet 1 2,3,4,5,………….

Balmer Series Visible 2 3,4,5,6,………….

Paschen Series Infrared 3 4,5,6,7,………….

Brackett Series Infrared 4 5,6,7,8,………….

Pfund Series Infrared 5 6,7,8,9,………….

Humphrey Series Infrared 6 7,8,9,10,………....

Concept of Limiting Lines
Spectral Series Line of maximum Line of Minimum
wavelength wavelength
Or Line of Minimum Or Line of maximum
Frequency Frequency

Lyman Series n1 = 1, n2 =2 n1 = 1, n2 = infinity

Balmer Series n1 = 2, n2 =3 n1 = 2, n2 =infinity

Paschen Series n1 = 3, n2 =4 n1 = 3, n2 =infinity

Brackett Series n1 = 4, n2 =5 n1 = 4, n2 =infinity

Pfund Series n1 = 5, n2 =6 n1 = 5, n2 =infinity

Humphrey Series n1 = 6, n2 =7 n1 = 6, n2 =infinity

 Draw backs of Bohr’s Model Sommerfield’s Concept
• The electron, in addition to the circular orbits
• It is only applicable to single electron species.
• It gives 2D- picture of the atom.
• It gives 2D- picture of the atom.
• It does not explain the Stark and Zeeman Effect.
• It does not explain the Stark and Zeeman Effect.
• No explanation for fine spectrum .
• No explanation for fine spectrum .
• It is not accordance with a Broglie’s dual nature of
• It is not accordance with a Broglie’s dual nature of
atom.
atom.
• It is not accordance with Heisenberg’s uncertainty
• It is not accordance with Heisenberg’s uncertainty
principle.
principle.
De Broglie’s Dual Nature of Matter
• All moving objects have a particles as well as the wave character.
• The wavelength associated with a moving particle is called De Broglie’s Wavelength (𝞴).
• Significant for microscopic particles like sub atomic particles, does not have significance in daily
life.
1 1
𝜆∝ 𝑜𝑟 𝜆 ∝ Relation Between 𝞴 and Accelerating Potential
𝑃 𝑚𝑣
h h • If a particle of charge q is accelerated through potential
𝜆 ∝ 𝑜𝑟 𝜆 ∝
𝑃 𝑚𝑣 difference of V,
Relation Between 𝞴 and Kinetic Energy ℎ
𝜆=
1 2𝑚𝑞𝑣
𝜆= 𝐾𝐸
2𝑚

2
p = 2mKE
 Heisenberg’s Uncertainty Principle
• It is impossible to measure simultaneously both the position and momentum of the particle, with
absolute accuracy.

ℎ
Δ𝑃 ⋅ Δ𝜘 ≥
4𝜋
Where., 𝜟P = uncertainty in momentum
𝜟x = uncertainty in position
h = Planck’s Constant

ℎ
Δ𝑃 ⋅ mΔv ≥
4𝜋
𝜟 v = uncertainty in velocity
Wave Mechanical Model of Atom

• The classical mechanics could not describe the behavior of electrons correctly.
• A model was proposed which could incorporate uncertainty principle and dual nature of matter.
• This approach was called quantum mechanics or wave mechanics.
• Developed independently by Heisenberg and Schrodinger.
• Schrodinger described the behavior of electrons in the form of mechanical equation called Schrodinger wave
equation.
𝜕2𝜓 𝜕 2 𝛹 𝜕 2 𝜓 +8𝜋 2 𝑛 • E = total energy of electron
+ + 𝐸−𝑣 𝜓=0 • V = Potential energy of
𝜕𝑥 2 𝜕𝑦 2 𝜕𝑧 2 ℎ2
electron
• 𝜓 depends upon the co-
ordinate of the principle.
• Square of the wave
amplitude at any point is
considered as the intensity of
the effect at that point.
Quantum Numbers
There are a set of four numbers assigned to describe electron in an atom.
• Principal quantum number (n)
• Azimuthal quantum number (l)
• Magnetic quantum number (m)
• Spin quantum number (s)
Principal Quantum Number
• It was given by Bohr
• Provide information about number of shells to
which electron belongs.
• Its values can be 1,2,3,……
• Its values correspond to K, L, M,.……………
• Larger the value of n, greater the distance of
electron from the nucleus.
• Maximum number of electron in a shell can be
2𝑛2 .
 Azimuthal Quantum Number 𝑙 Sub-shell
• Also called angular quantum number or subsidiary quantum number. 0 s Sharp
• Stated by Sommerfield. 1 p Principle
• For every value of n, l can be 0, …… (n-1).
2 d Degenerate
• It is an explanation for fine spectrum.
3 f Fundamental
• Value of l corresponds to the subshell or sub level of energy within the shell.
4 g Generalised
• Order of energy f > d > p > s.
• As the value of l increases the distance of given subshell from the nucleus also
increases.
• Total number of value of l or a number of subshell in a shell = n.
• Orbital angular momentum of electron is given as.
𝒉
𝝁 = 𝒏 𝒍 𝒍 + 𝟏 = 𝟐𝜫 𝒍 𝒍 + 𝟏

• Maximum number of electrons that can be present in sub-shell is given by (2l

+1)
Magnetic Quantum Number
• It is explanation for Zeeman effect.
• It gives the number of preferred Subshell 𝑙 m Orientation
orientation of electron in the s
presence of magnetic field which are s 0 0 1
called orbitals. orientations
• It was sated by Linde.
p 1 -1, 0, +1 3
• For every value of 𝒍, m can be from -
orientations
𝒍 to +𝒍, 𝒕𝒉𝒓𝒐𝒖𝒈𝒉 𝒛𝒆𝒓𝒐.
• Total value of m for energy value of 𝒍 d 2 -2, -1, 0, +1, +2 5
are (2𝒍 +1). orientations
• Orbitals of the same sub-shell have f 3 -3, -2, -1, 0, +1, +2, +3 7
same energy are known as orientations
degenerate orbitals.
• Number of orbitals in a given shell is
given by 𝒏𝟐 .
 Spin Quantum Number
• The idea of electron was advanced by Unlenbeck and Gold Smith.
• An electron revolves around the nucleus and also spins about its own axis.
• Spin produces angular momentum in a particular direction.
• s = + ½ for clockwise spin.
• s = - ½ for anticlockwise spin.
• According to modern Quantum theory , spin angular momentum is equal
ℎ
to 𝑠 𝑠+1 .
2𝜋

• Spin multiplicity is given by [2∑ s+1].

Rules for the filling of electrons
• Pauli’s Exclusion Principle
• Aufbau Principle
• Bohr Bury rule : ( n+l ) rule
• Hund’s Rule of Maximum Multiplicity

Pauli’s Exclusion Principle

Aufbau Principle Hund’s rule
 Photo electric Effect

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