CHAPTER-4
ATOMIC STRUCTURE
Prepared By – Dawit Adane
Historical Background of Atomic Structure
The earliest models of the atom were developed by the
ancient Greek philosophers
Empedocles (about 440 B.C.) stated that all matter was
composed of four “elements” – earth, wind, fire and water.
Democritus (about 470-370 B.C.) thought all forms of
matter were composed of tiny indivisible particles, called
atoms, derived from the Greek word “Atomos”
John Dalton’s Atomic Theory
Elements are composed of smaller/minute, indivisible
particles called atoms.
Atoms cannot be created, divided into smaller particles, nor
destroyed in the chemical process
Atoms of the same element are identical. They have the
same mass and chemical properties.
But Isotopes of elements exist today’s
Atoms of different elements are different. They have
different masses and chemical properties
Isotopes like C-14 and N-14 make this incorrect
Chemical compounds are formed by the union of two or
more atoms of different elements. When atoms of different
elements combine to form a compound, they do so in a
Cont’d
Cannonball atomic model (John Dalton, 1803)
Modern Atomic Theory
The Thomson’s/Plum Pudding Atomic Model
Atoms can be broken down into smaller, more
fundamental particles
Electrons: negatively charged subatomic particles.
Thomson (English physicist) discovered electrons in 1897
How did he discover electrons?
Passed electric current through gases at low pressure. The
sealed gases in glass tubes fitted at both ends with metal
disks called electrodes. Electrodes were connected to a
source of high-voltage electricity. One electrode, the
anode, became positively charged other electrode, the
cathode, became negatively charged.
A glowing beam formed between the electrodes, called a
cathode rays.
A beam of rays came out from the cathode (cathode rays)
and hit the anode.
►Cathode rays were always deflected by an electric field
from the negatively charged plate inside the cathode ray
tube, which led him to conclude that the rays carried a
negative electric charged particles called electrons.
Thomson’s Atomic Model
Thomson believed that the electrons were like plums
embedded in a positively charged “pudding,” thus it was
called the “plum pudding” model.
►An atom consists of negative charges scattered throughout a
ball of positive charges.
The positively charged sphere is balanced electrically by
negatively charged electrons (atomic neutrality).
Drawback
J.J. Thomson Model can’t explain
►Spectral lines (according to this model, radiation emitted
should be monochromatic; however, experiments with
hydrogen shows a series of lines falling into different parts
of the electromagnetic spectrum)
►Radioactivity (nature of emitted rays and their origin in the
atom)
►Scattering of charged particles by atoms
Nuclear Atom – Rutherford Planetary Model
►Protons and neutrons make up the dense, positive nucleus
because proton have positive charge and neutrons have no
charge (neutral) and the nucleus is located in the center of
the atom.
►Almost all of the atom’s mass is located in the nucleus.
►Atom is mostly empty space with the electrons moving
around outside the nucleus.
A neutral atom contains the same number of electrons and
protons.
Rutherford’s Scattering Experiment
►Alpha particle are helium atoms that have lost their two
electrons and have a double positive charge because of the
two remaining protons
► A thin gold foil was bombarded with a beam of fast-
moving α-particles (+ve charged) - He+
Experimental Result and Conclusion
Most α-particles passed through the foil without deflection
Some α-particles were scattered at different angle and even
very few α-particles rebounded back
The great majority of alpha particles passed straight through
the gold atoms without deflection – the atom is mostly
empty space.
A small fraction however bounced off the gold foil at very
large angles, even straight back – all the positive charge and
almost all mass are concentrated in a small region that has
enough positive charge to account for the great deflection of
some of the alpha particles.
Number of positive charges in each nucleus can be calculated
from experimental results is Presence of protons in nucleus
Cont’d
Nucleus is positively charged because it repels the
positively charged alpha particles.
Nucleus is relatively massive and highly charged because of
the large angle deflection.
Also, Rutherford Postulated the presence of neutrons in the
nucleus.
Electron Orbits
Since the electrons are in circular motion at a relatively
great distance, dynamically stable orbits are formed by
balancing the centrifugal force acting towards outside and
the electric force pulling them to the nucleus.
The centrifugal force
The electric force where z is the no. of protons
The condition for a dynamically stable orbit is
►The electron velocity is
Electron Orbits
►The total energy E of the electron in a hydrogen atom is the
sum of its kinetic and potential energies, which are
Substituting for v results
where, Z is the atomic number.
Note that the total energy is negative, indicating a bound
electron–proton system. This means that energy in the amount
of ET must be added to the atom to remove the electron to
infinity and leave it motionless.
The Drawback/Failure of Rutherford’s Model
►How are the electrons (negatively charged bodies) held
outside the nucleus (a positively charged body) despite the
attractive electrostatic force? According to the planetary
model electrons are revolving around the nucleus like
planets around the Sun, though planets are electrically
neutral and thus stay in their orbits. According to classical
electromagnetic theory, any charge placed in circular motion
will radiate light (electromagnetic energy), which means
that electrons orbiting around the nucleus would spiral
inward and collapse into the nucleus due to the loss of
kinetic energy. This would produce extremely unstable
atoms.
Cont’d
►The radiated energy of photons from spiraling electrons
would change in frequency during the deceleration process
and produce a continuous spectrum; however, at that time,
the spectra of some of the elements were known to show
specific discrete lines. Thus, he don’t explain about the line
spectra.
►does not say anything about the way the electrons are
distributed around the nucleus.
►What does hold the positive charges in the nucleus together
in spite of the repulsive electrostatic forces?
The Bohr Model
In 1913, Niels Bohr introduced his atomic model based on
the simplest atom, hydrogen (only 1 electron)
Bohr proposed that an electron is found only in specific
circular paths, or orbits, around the nucleus
Cont’d
• By applying Planck’s ideas of quantized energy levels to
orbiting atomic electrons (electrons could move in certain
orbits without radiating. He called these orbits stationary
states) and Einstein’s concept of the photon (the atom
radiates when the electron makes a transition from one
stationary state to another), he overcame the problem of a
classical electron that continually lost energy and explain in
detail about the observed line spectra of an element.
Postulates of Bohr
1. The electron moves in circular orbits about the proton
under the influence of the Coulomb force of attraction and
Newtonian centrifugal force.
2. Only certain orbits are stable. These stable orbits
(stationary states) are ones in which the electron does not
radiate. Hence the energy is fixed or constant in time, and
ordinary classical mechanics may be used to describe the
electron’s motion in these stable orbits.
Postulates of Bohr
3. Radiation is emitted by the atom when the electron “jumps”
from a more energetic (higher energy level) initial
stationary state to a less energetic lower final state and
when the atom absorbs right amount of radiational energy,
the electron “jumps” from an initial lower energy level to
higher final energy level. The frequency f of the photon
emitted in the jump is independent of the frequency of the
electron’s orbital motion. Instead, the frequency of the
radiation emitted/absorbed is related to the change in the
atom’s energy and is given by the Planck–Einstein formula:
Postulates of Bohr
4. The size of the allowed electron orbits is determined by an
additional quantum condition imposed on the electron’s
orbital angular momentum. Namely, the allowed orbits are
those for which the electron’s orbital angular momentum
about the nucleus is an integral multiple of ,
Where, n is the principal quantum number.
Thus, the velocity of the electron in the stationary orbit is:
Electron Orbits
Since the electrons are in circular motion at a relatively
great distance, dynamically stable orbits are formed by
balancing the centrifugal force acting towards outside and
the electric force pulling them to the nucleus.
The centrifugal force
The electric force where z is the no. of protons
The condition for a dynamically stable orbit is
►The electron velocity in the stable orbit is
Electron Orbits
►The total energy E of the electron in a hydrogen atom is the
sum of its kinetic and potential energies, which are
Substituting for v results the total energy as:
where, Z is the atomic number.
Note that the total energy is negative, indicating a bound
electron–proton system. This means that energy in the amount
of ET must be added to the atom to remove the electron to
infinity and leave it motionless.
Quantization
Equating the two expression of velocity of the electron
results for the expression of orbital radius and then the
allowed energy levels:
The orbital radius is then,
• The above equation shows that only certain orbits are
allowed, quantization of orbital radii.
The smallest radius occurs for n = 1 & Z = 1, is called the
Bohr radius, and is denoted a0.
Quantization
Thus, the allowed quantized orbital radius can be written in
short as:
The quantization of the orbit radii immediately leads to
energy quantization. Thus, the allowed energy levels are:
For, n = 1 & Z = 1, En = E0 = - 13.61 eV, then
• The integers n corresponding to the discrete, or quantized,
values of the atom’s energy have the special name quantum
numbers.
Characteristics of Bohr’s Postulate
Electrons can not be exist between energy levels.
The higher the energy level, the farther it is from the
nucleus.
Electrons can jump from one energy level to another.
An electron to transit from one energy level to another, the
electron must gain or lose the right amount of quantum of
energy equal to the energy difference between energy levels.
If an electron gain/absorb energy, then it jump to higher
energy levels (away from nucleus)
If an electron lose energy, then it jump to lower energy
levels (closer to nucleus) and emit radiation.
The amount of energy required/released during the transition
from one energy level to another is not same for the
electrons found in different energy levels.
Characteristics of Bohr’s Postulate
Higher energy levels (outer orbits) are closer together. This
means an electron absorbs/releases less amount of energy
during transition between higher energy levels since the
energy difference between energy levels is getting smaller and
smaller as we move further away from the nucleus.
• When electrons are in the lowest stationary (non-radiating)
energy levels, they are said to be in the ground state.
• When energy from a flame or other source is absorbed by the
electrons, they are promoted to a higher energy level (excited
state).
• The minimum energy required to ionize the atom (that is,
to completely remove an electron in the ground state from
the proton’s influence) is called the ionization energy.
Atomic Emission Spectra
When atoms absorb energy, electrons move into higher
energy levels. These electrons then lose energy by emitting
light when they return to lower energy levels.
In the Bohr model, the lone electron in the hydrogen atom
can have only certain specific energies.
When the electron has its lowest possible energy, the atom
is in its ground state.
Excitation of the electron by absorbing energy raises the
atom from the ground state to an excited state. A quantum of
energy in the form of light is emitted when the electron
drops back to a lower energy level.
Atomic Emission Spectra
The light emitted by an electron moving from a higher to a
lower energy level has a frequency directly proportional to
the energy difference between the electron’s transition
orbital.
In terms of wavelength λ,
Where R = Rydberg constant = 1.0973732 x 107 m–1.
The three groups of lines in the hydrogen spectrum
correspond to the transition of electrons from higher energy
levels to lower energy levels.
Cont’d
Energy Level Diagram
1 1 1
R 2 2
n n
f i
n= 0
n=5 -0.54 eV
Brackett
n=4 -0.85 eV
Panchen
n=3 -1.51 eV
Balmer
n=2 -3.40 eV
Lyman
n=1 -13.6 eV
Limitations of Bohr’s Model
• Calculations of energy and radii worked only on single-
electron atoms or ions (hydrogen and hydrogenic ions). The
Bohr model was tested with the hydrogen element but failed
to explain the energies absorbed and emitted by atoms with
more than one electron.
• Could not account for the intensities of the fine structure of
the spectral lines.
• Could not explain the binding of atoms into molecules. For
example: carbon has 2 unpaired electrons, why does it form
4 bonds?
• What does hold the positive charges in the nucleus together
in spite of the repulsive electrostatic forces?
Bohr’s Correspondence Principle
Bohr’s Correspondence Principle states that quantum
mechanics is in agreement with classical physics when the
energy differences between quantized levels are very small
Similar to having Newtonian Mechanics be a special case of
relativistic mechanics when v << c
The greater quantum number, the closer quantum physics
approaches to classical physics.
The Quantum Mechanical Model
The quantum model determines the allowed energies of an
electron can have probabilistically, i.e. how likely it is to
find the electron in various locations around the nucleus
De Broglie suggested that electrons be considered waves
that are confined to the spaces around the nucleus.
The cloud is more dense where the probability of finding
the electron is high.
The orbital of an electron is a 3D
region/shape of volume around
the nucleus where the probability
of finding the electron
is about 90 % (boundary shape).
Principles QM Theory of Atoms Based ON
De Broglie matter wave
Max Born’s probabilistic interpretation of representation of
wave function of matter wave
Heisenberg uncertainty principle
Schrodinger wave Equation
Shell (Energy level) → Sub-shell → Orbital → State
Quantum Numbers
The set of integers that label the discrete values of important
atomic quantities, such as energy and angular momentum.
Numbers used to specify the properties of atomic orbitals
and properties of electrons in those orbitals.
There are 4 quantum numbers:
Principal Quantum Number
Orbital Quantum Number
Magnetic Quantum Number
Spin Quantum Number
Quantum Theory:- mathematically describes the wave
properties of electrons.
Quantum theory determined that the wave equations give
only the probability of finding an electron at a given place.
Principal Quantum Number (n)
Represents the main energy level (shell) of the electron and
its distance from the nucleus.
Indicates about quantization of energy
It determines the energy and size of the orbital.
Equation: - shows how many electrons can be in each
energy level
All are whole numbers, n = 1, 2, 3, …
As n increases, the energy and average distance from the
nucleus increases.
Angular Momentum(Orbital) Quantum Number ℓ
indicates the shape of an orbital (sub–shells)
The number of orbital shapes possible is equal to n – 1.
The values of ℓ can range from 0 to n – 1 in integer steps
The value of ℓ is then assigned by a letter:
ℓ=0 s ℓ=4 g
ℓ=1 p ℓ=5 h
ℓ=2 d
ℓ=3 f
In the Bohr theory, the angular momentum of the electron
was quantized according to the relation L = nħ
The solution of the Schrödinger wave equation gives the
relation for the angular momentum:
Orbital Shapes
Different atomic orbitals are denoted by letters.
The s orbitals are spherical, and p orbitals are dumbbell-
shaped.
Four out of the five d orbitals have the same shape (clover
shaped) but different orientations in space.
Orbital Shapes
The f orbitals is really complex.
s- orbitals shape p- orbitals shape
d-orbital
Orbital Shapes
The Five d – orbitals
Orbital Shapes
The Seven F – orbitals
Magnetic Quantum numbers -
This number describes orientations of the orbitals that each
sublevel (subshell) can have and
It also describes the number of orbitals in each sub shell.
In each s sublevel, there is only 1 orientation (1 orbitals)
because it’s a sphere
In a p sublevel, there are 3 orientations (3 orbitals) because
the dumbbell can be aligned on the x, y or z-axis.
In a d sublevel, there are 5 orientations (5 orbitals).
In an f sublevel, there are 7 orientations (7 orbitals).
The range of = –ℓ to 0 to +ℓ
Each orbital in each subshell maximumly contains two
electron (pair of electron).
Spin Quantum Numbers ()
This number describes the spin of the electrons about its
axis in an orbital.
There can be two electrons in each orbital as long as they
are spinning in opposite directions.
The spin quantum number can have only 2 possible
fractional values: = +1/2 or -1/2, which indicate direction
of spin moment.
A single orbital can hold a maximum of 2 electrons which
must have opposite spins
Electron Configurations
The ways in which electrons are arranged in various
orbitals around the nuclei of atoms are called electron
configurations.
The electron configuration of an atom is a shorthand
method of writing the location of electrons by energy levels,
sublevels and orbitals
Shell (Energy level) → Sub-shell → Orbital → State
There are three rules used to determined the electron
configurations of atoms:-
The aufbau principle,
The Pauli exclusion principle, and
Hund’s rule
Aufbau Principle
According to the aufbau principle, in a ground state atom,
electrons occupy the orbitals of lowest energy level first.
In the aufbau diagram below, each box represents an atomic
orbital
Arrange the energy sublevels according to increasing
energy is: 1s 2s 2p 3s 3p 4s 3d …
Aufbau Principle
Fill each sublevel with electrons until you have used all the
electrons in the atom:
For example Fe = 1s2 2s2 2p6 3s2 3p6 4s2 3d 6
In noble gas notation Fe = [Ar] 4s2 3d 6
See the orbital diagram below
Pauli Exclusion Principle
The Pauli exclusion principle states that no two electrons in
an atom can exist in the same quantum state
Because the state of any electron is specified by the four
quantum numbers n, ℓ, , and , the exclusion principle states
that no two electrons can have the same set of the four
quantum numbers.
No two electrons in the same atom can have the same set of
four quantum numbers.
In other words, no two electrons can be in the same place at
the same time.
Hund’s Rule
Hund’s rule states that electron pairing happens only after
all the available degenerate (equal energy) orbitals are
occupied by one electron each with parallel spin.
Orbitals of equal energy are each occupied by one electron
before any orbital is occupied by a second electron.
Electrons occupy orbitals of the same energy in a way that
makes the number of electrons with the same spin direction
as large as possible.
Magnetism of The Atom
• The atoms filled with a paired electron orbitals in electronic
configuration are generally diamagnetic. Diamagnetic
materials has no response for external magnetic field.
• The atoms filled with at least one unpaired electron orbitals
in electronic configuration are called paramagnetic.
Paramagnetic materials has a weak interaction with external
magnetic field.
• Elements with odd number of atomic number have at least
one unpaired electron orbitals; thus, they are always
paramagnetic.
• Elements with even number of atomic number may or may
not have unpaired electron orbitals; thus, they can be either
paramagnetic or diamagnetic.
Periodic Table
Read About Periodic Table
Models of the Atom
Cont’d
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