Chapter Four: The Electronic Structure of Atoms

Chapter Four
The Electronic Structure of Atoms
3 August 2010 Dr. Raef A. Ahmed 1
From Classical Physics to Quantum Theory
Before year 1900, theories of different scientists:
¾ Rutherford’s Model Proposed Electron Orbits
¾ Bohr’s Model Confines Electrons to Energy Levels
¾ Thom son’s experiments demonstrated that electrons act
like particles that have mass. Although this mass is very small.
In the 1900 new era in physics started by a German Scientist
called Max Plank.
Plank has discovered that atoms and molecules emit energy only
in certain discrete quantities or quanta . Scientists had always
assumed that energy is continuous , which meant that any amount
of energy could be released in a radiation process. This theory is
called quantum theory.

Electrons Act Like Both Particles and Waves
In 1924, Louis de Broglie pointed out that the behaviour of
electrons according to Bohr’s model was similar to the
behaviour of waves.
De Broglie suggested that electrons could be considered
waves confined to the space around a nucleus. As waves,
electrons could have only certain frequencies.

A wave: is a vibrating disturbance by which energy is
transmitted.
The speed of the wave depends on the type of wave
and the nature of the medium through which the
wave is travelling.
Wavelength: is the distance between identical points on
successive waves. (Lambda λ)
The Frequency (ν nu): of the wave is the number of waves
that pass through a particular point in one second.
The amplitude: is the vertical distance from the midline of a
wave to the peak or trough.
Amplitude
Amplitude
Wavelength
Direction of wave
propagation
wavelength
Amplitude
Speed of the wave u = λν
The wavelength express the length of the wave or
distance/wave. The frequency indicates the number of
these waves that pass any reference point per unit of time
or waves/time.
Wavelength is usually expressed in units of meters,
centimetres or nanometres.
Frequency is measured in hertz (Hz)
1 Hz = 1 cycle/s “the word cycle may be
left. For example, 25/s”.
Electromagnetic Radiation
The radiant energy also called electromagnetic radiation
moves at speed of about 3.00 × 108 m/s through vacuum
which is called the speed of light (c). The waves associated
with electromagnetic radiation is called electromagnetic
waves. The fig. Below shows the various types of the
electromagnetic radiation/electromagnetic spectrum.
Different types of radiation differ from one another in wavelength

and frequency. The long radio waved are emitted by large antennas,
such as those used for broadcasting stations.
The shorter, visible light waves are produced by the motion of
electrons within atoms and molecules.
our eyes are sensitive to only a small portion of the electromagnetic
spectrum. This sensitivity ranges from 700 nm, which is about the
value of wavelengths of red light, to 400 nm, which is about the value
of wavelengths of violet light.
Planks Quantum Theory
When Solids are heated they emit radiation over a wide
range of wavelength. Such as the bright white light of the
tungsten and the red glow of a heater.
From the classical physics it was believed that atoms and
molecules could emit or absorb any arbitrary amount of
radian energy.
Plank said that atoms and molecules could emit or absorb
energy only in discrete quantities, like small packages.
Plank gave name quantum to the smallest quantity of
energy that can be emitted or absorbed in the form of
electromagnetic radiation
The energy E of a single quantum =
E= hν
Where h is called Planks constant = 6.63 × 10‐23 J.s
According to this quantum theory, energy can be emitted in
multiples of hν, for example, hν, 2 hν, 3 hν…… but never 1.5
hν or some other fraction. This is called quantization of
energy.
The concept of quantization was very new and shocking
even Planks himself could not explain why energy should be
quantized or fixed when he presented his theory.
The Photoelectric Effect
This is a phenomenon in which electrons were ejected
from the surface of a certain metals when they exposed
to light of at least a certain minimum frequency, called
threshold frequency.
The number of ejected electrons was proportional to the
intensity of the fallen light but energies of the ejected
electrons were not.
In year 1905 Albert Einstein solved the mystery of the
photoelectric effect where the normal wave theory fail
Einstein suggested that a beam of light is a stream of particles
These particles of light are called photons.
Einstein proposed that light has the properties of both waves
and particles.
E of the photon is given by Planks E =hν
Electrons are held in a metal by attractive force. To remove
them we must employ light of a sufficiently high frequency.
Therefore shining a beam of light onto a metal surface can
be thought of as shooting a beam of particles‐photons at the
metal atoms.
E =hν = KE + BE
This means that, if the frequency of a photon is such that hν
is exactly equal to the binding energy (BE) of the electrons
in the metal, then the light will have just enough energy to
loosen the electron in their place without removing them.
But, if the frequency is higher then the electrons themselves
will acquire some Kinetic energy (KE)and leave the metal.
So we can rearrange the equation to get KE as:
KE = hν – BE
The more energetic the photon is (higher frequency), the greater the
KE of the ejected electron. Also, the more intense the light, the greater
the number of electrons emitted by target metal. The higher the
frequency of the light the greater the KE of ejected electrons.
Bohr’s Theory of the Hydrogen Atom
Emission Spectra: it can be either continuous or line spectra
of radiation emitted by substance.
This can happened by energizing a sample of material with
thermal energy or some other form of energy. Such as a
red‐hot or white‐hot iron bar. The red color glowing you see
is portion of its emission spectra that sensed by eye. This is
continuous emission i.e that is all wavelengths of light are
represented in the spectra.
In gas phase atoms do not show continuous spread of
wavelength from red to violet (continuous emission).
Gases emit light only at specific wavelength
This is called line spectra. It shows a bright lines in the spectra.
Every element has a unique emission spectra.
Emission Spectrum of Hydrogen Atom
When a high‐voltage current is passed through a tube of
hydrogen gas at low pressure, lavender‐colored light is seen.
In 1913, Bohr showed that hydrogen’s line‐emission
spectrum could be explained by assuming that the hydrogen
atom’s electron can be in any one of a number of distinct
energy levels or quantized (fixed value of energy).

The electron can move from a low energy level to a
high energy level by absorbing energy. Electrons at
a higher energy level are unstable and can move to a
lower energy level by releasing energy (giving up
quantum of energy or photon). This energy is released
as light that has a specific wavelength. Each different
move from a particular energy level to a lower energy
level will release light of a different wavelength.
Bohr developed an equation to calculate all of the possible
energies of the electron in a hydrogen atom:
1
En = ‐ RH ( )
n2
∆E = Ef – Ei
1 1
∆E = RH ( )
ni2 ‐ nf2
Where RH the Rydberg constant = 2.18 × 10‐18 J. The

number n is an integer called principle quantum number
Energy of a free electron is Zero
Ground State or Ground level: refers to the lowest
energy state of a system (which is atom and n=1).
Excited state or excited level: which is higher in energy than
the ground state.
Radius of the orbit depends on n2. So, the higher the excited
state, the further way the electron from nucleus.
The emission spectrum of hydrogen covers a wide range of
wavelength from infrared to the ultra violet. The various
series of transition in the hydrogen spectrum are:
Series nf ni Spectrum region
Lyman 1 2,3,4,...... Ultraviolet
Balmer 2 3,4,5,....... Visible and Ultraviolet
Paschen 3 4,5,6,......... Infrared
Brackett 4 5,6,7,...... Infrared
Quantum Mechanics
Bohr’s theory could not explain the emission spectra of atoms
containing more than one electron such as atoms of helium
and lithium.
Heisenberg uncertainty principle: it is impossible to know
simultaneously both the momentum (mass times velocity) and
the position of a particle with certainty.
Schrödinger Equation: It is equation formulated by
Schrödinger using advanced calculus to solve the problem of
the behaviour of particle. It incorporates both particle
behaviour in term of mass m, and wave behaviour, in term of
a wave function ψ (psi).
Quantum mechanical Treatment of the Hydrogen Atom
We can not specify the exact position of an electron in an
atom, however we can define the region where the electron
might be at a given time. This is called:
Electron density: gives the probability that an electron will be
found in a particular region of an atom.
Atomic orbital
a region in an atom where there
is a high probability of finding
electrons
Quantum numbers
These are the numbers required to describe the distribution
of electrons in hydrogen and other atoms. These numbers are
derived from Schrödinger equation. They are four numbers:
1) Principle quantum number (n).
2) The angular momentum quantum number (l).
3) Magnetic quantum number (ml).
4) Spin quantum number (ms).
Principle quantum number (n).
It can have integral value 1,2,3,........ It relates to the
average distance of the electron from the nucleus in a
particular orbital. The larger the value of n the further the
electron from the nucleus and therefore, the larger the
orbital and electron’s energy increases.
The angular momentum quantum number (l).
This number tells us the “shape” of the orbital. The value of
(l) depends on n.
(l) Has a possible values from 0 to (n‐1).
Fro example: if n =1 then (l) = n – 1= 1 – 1 =0 only one value
If n = 2 then, (l) = 2 ‐1 = 1 which means that (l) has
two possible value: 0 and 1.
If n = 3, then (l) has 3 values, which are n – 1 = 3 ‐1 = 2 so
the values of (l) are: 0, 1, 2
(l) 0 1 2 3 4 5
Name of s p d f g h
Orbital
A collection of orbital's with the same value of n called
“shell”.
Example, shell with n= 2 compose of two sub shell, (l) = 0,
(l)= 1. These subshells are called 2s and 2p.
Magnetic quantum number (ml).
This quantum no. describes the orientation of the orbital
in space. The value of (ml) depends on the value of (l). So,
for certain value of (l) there (2 l + 1) of (ml) values,
-l, (‐l + 1)....0, ......(+l – 1), + l
Example : If l = 0, then ml = 0.
If l = 1, then there are [(2 × 1) + 1] = 3 so, 3 values
for ml = ‐1, 0, +1
If l = 2, then ml values are [( 2 × 2) + 1] = 5

5 values which are:
‐2, ‐1, 0, +1, +2
If we have n = 2, l = 1, so we have 2p subshell and in this

subshell there are three 2p orbital's (this is from ml)
The electron Spin quantum number ms
Electrons act as a tiny magnet. They can spin on their own
axes like earth.
Spinning create magnetic field.
Two spinning motion are allowed. One is clockwise and the
other is anticlockwise.
The electron spin have a value either + ½ or ‐ ½
A single orbital can hold a maximum of two electrons, which
must have opposite spins.
Atomic Orbital
Electrons can be any where around nucleus but most of
the time close to the nucleus. The electron density falls off
as the distance from the nucleus increases.
Shape of s‐Orbital
s‐orbital is spherical and enclose 90% of the total electron
density in the orbital. All s‐orbital's are spherical in shape
but differed in size with increase of n.
p‐orbital
Starts with n= 2. when n =1, l = 0 so, there is only 1s.

When l = 1, the ml can have ‐1, 0, +1 so we have 3
values.
This is called 2p and the 3 values represent the orbital's:
2px, 2py, 2pz .
These orbital's are identical in size, shape and energy.
They differ in the orientation along axes.
Each p orbital looks like two lobs on opposite sides of the
nucleus. See fig.
d‐orbital
l = 2, there are 5 values for ml, which corresponds to 5 d‐
orbital’s. The lowest value of n for the d‐orbital is 3.
So, n =3, l = 3‐1=2 so ml = 2 l + 1 = 5.
ml has 5 values. Therefore, the 3d has: 3dxy, 3dyz, 3dxz,
3dx2‐y2, 3dz2.
As before, all the 5d‐orbitals are identical in energy but
differ in orientation. See figure on the next slide
Example: List the values of n, l and ml for orbital's in
the 4d subshell.
Ans: As we saw, the number given in the designation of the
subshell is the principle quantum no. n. So, n = 4. For d
orbital , l = 2. The value of ml can vary from –l to l.
Therefore, ml can be ‐2, ‐1, 0, 1, 2 (which corresponds to the
five d orbital's)
Example, what is the total orbital’s associated with n= 3?
Ans: For n =3, The possible values of l are 0, 1, 2. Thus we
have s, p and d. They all will have same n = 3 so, 3s, 3p and
3d. Thus, there are one 3s orbital (n=3, l= 0, ml = 0), three
3p orbital’s (n= 3, l = 1 and ml= ‐1, 0, +1); there are
five 3d orbital’s (n = 3, l = 2 and ml = ‐2, ‐1, 0, +1, +2)
Therefore, the total number of orbital’s = 1 + 3 + 5 = 9
Energies of Orbital's
In hydrogen atom the energy of an electron in orbital is
determined solely by its principle quantum number. So
the energies of hydrogen atom increases as fellows:
1s<2s = 2p< 3s =3p =3d<4s=4p=4d=4f<
The energy picture is more complex for many
electron atoms (atoms with more than one
electron).
The important idea is: In many electron atom, for a given
value of n, the energy of an orbital increases with increases
of l.
The total energy of an atom depends not only on the sum of
the orbital energies but also on the repulsion between the
electrons in these orbital's (each orbital cal accommodate
up to 2 electrons).It turns out that the total energy of an
atom is lower when 4s subshell is filled before 3d subshell.
1s
2s 2p
3s 3p 3d
4s 4p 4d 4f
5s 5p 5d 5f
6s 6p 6d
7s 7p
1s <2s<2p<3s<3p<4s<3d<4p<5s<4d<5p<6s<
4f<5d<6p<7s<5f<6d<7p
Electron configuration
The four quantum numbers are the address of the
electron. It enables us to specify the location of the
electron in atom. The simplified way of presenting the
values of the four numbers of an electron as (n, l, ml, ms).
For example the four quantum numbers for a 2s orbital's
are: n =2, l = 0, ml = 0, ms = + ½ or ‐ ½. We write them as:
(2, 0, 0, + ½) or (2, 0, 0, ‐ ½)
Electron configuration of the atom is how the
electrons are distributed among the various atomic
orbital’s.
Denotes the number of electrons in
the orbital or subshell
Denotes n 1s1
Denotes l
H = 1s1
Orbital diagram
Pauli Exclusion principle
No two electrons in an atom can have the same four
quantum numbers (This is for the many electron atoms). So,
if two e‐ in an atom have same n, l, and ml (that is, these
two electrons are in the same atomic orbital), then they
must be different in the ms values.
He has two electrons and the can be represented such as:
He a) Both electron (1, 0, 0, +1/2)
a
b) Both electron (1, 0, 0, ‐1/2)
b c
c) One e‐ is (1, 0, 0, +1/2) and
the other is (1, 0, 0, ‐1/2)
Paramagnetism and diamagnetism
If two e‐ in the orbital have same or parallel spin ( or );
their net magnetic field would reinforce each other. This
arrangement would make the atom paramagnetic means
attracted by a magnet (Case A)
N N N N
A B
S S S S
On the other hand if the two e‐ are anti parallel then the
magnet effect cancel out and the atom is called
diamagnetic means repelled slightly by magnet (case B)
Generally we can say that if the atom has an odd
number of e‐ then it must be Paramagnetic. If it has
an even number of e‐, it could be paramagnetic or
diamagnetic
Hund’s Rule:‐ look at the carbon electron config. (Z=6) = 1s2
2s2 2P2 . The orbital diagram for the p orbital:
(a) (b) (c)

Non of the arrangements violates Pauli exclusion principle but
which arrangement is the most stable?!
Hund’s Rule: The most stable arrangement of electrons in sub
shell is the one with the greatest number of parallel spins.
So, c arrangement satisfy this condition means it is the
most stable.
Nitrogen : Z= 7, e‐ Config. 1s2 2s2 2p3
N Paramagnetic
Oxygen: Z= 8, e‐ config: 1s2 2s2 2p4

O Paramagnetic
Neon : Z= 10, e‐ Config. 1s2 2s2 2p6
Ne Diamagnetic
Summary for electron configuration in ground state
in atom
1) No two e‐ in the same atom can have the same four Q.N. (Pauli exclusion
principle).
2) Each orbital can be occupied by maximum of two e‐. They must have
opposite spins.
3) Maximum no. of e‐ that an atom can have in a principle level n is to use the
formula 2n2 (e.g: if n= 4 then there are 32 electron in that level)
4) The most stable arrangement of e‐ in a subshell is the one that has the
greatest number of the parallel spins. (Hund’s Rule)
5) Atoms in which one or more e‐ are unpaired are paramagnetic . Atoms in
which all the electrons spins are paired are diamagnetic.
6) In H atom, the energy of an e‐ depends only on its principal Q.N. n. In many
electron atom, the energy of an e‐ depends on both n and l.
7) For e‐ of the same principal Q.N., their penetrating power or proximity to
the nucleus decrease in order s>p>d>f. More energy need to separate 3s e‐
than need to remove a 3p electrons.
The building up principle
Aufbau principle: dictates that as protons are added one by
one to the nucleus to build up the elements, electrons are
similarly added to the atomic orbital's.
Condensed Electronic configuration
Noble gas core. The element that
precedes the element being considered
Na: [Ne]3s1
Valance electrons, which
comes after the noble gas
core
K : [Ar]4s1
See the electronic configuration of most of the elements in
the book page 220
Transition metals: either have incomplete filled d
subshells or readily give raise to cations that have
incompletely filled d subshell.
Some irregularities appears in
Cu: [Ar]4s13d10 the e‐ config. here. The reason
is that more stability for the
atom with half filled (3d5) and
completely filled (3d10)
Lanthanides or rare earth series: they have incompletely
filled 4f or readily give raise to cations that have
incompletely filled 4f subshell.
Kr = Krypton, Xe= Xenon, Rn= Radon some rare gases used as
core

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Chapter Four

3 August 2010 Dr. Raef A. Ahmed 2

3 August 2010 Dr. Raef A. Ahmed 3

Different types of radiation differ from one another in wavelength

3 August 2010 Dr. Raef A. Ahmed 16

Where RH the Rydberg constant = 2.18 × 10‐18 J. The

Lyman 1 2,3,4,...... Ultraviolet

Balmer 2 3,4,5,....... Visible and Ultraviolet

Paschen 3 4,5,6,......... Infrared

Brackett 4 5,6,7,...... Infrared

If l = 2, then ml values are [( 2 × 2) + 1] = 5

If we have n = 2, l = 1, so we have 2p subshell and in this

Starts with n= 2. when n =1, l = 0 so, there is only 1s.

1s<2s = 2p< 3s =3p =3d<4s=4p=4d=4f<

(a) (b) (c)

Oxygen: Z= 8, e‐ config: 1s2 2s2 2p4

Neon : Z= 10, e‐ Config. 1s2 2s2 2p6

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