CHAPTER 2

ELECTRONIC
STRUCTURE
OF ATOMS
 What happens when
someone switches on a
neon light?
• Electrons in the neon atoms are
excited to a higher energy by
electricity
•An electron can remain in a higher-
energy state for not only a very short
time, and it emits light when it
returns to a lower energy
Light, Photon Energies
and Atomic Spectra
• Eerie phenomenon of the
aurora borealis.
• Relate with the generation of
light and its transmission
through space.
Electronic structure
❖ Refers to the number of electrons in the
atom as well as their distribution around
the nucleus and their energies.
❖Quantum theory: explains much of the
behaviour of electrons in atoms
❖The quantum description of the
electronic structure of atoms help us to
understand the arrangement of the
elements in the periodic table
 Background: basic structure
Sub-atomic particles include: Protons (p+), neutrons (n) and electrons (e–)
n: neutral, massive, in nucleus,
e–: -ve, small mass, orbits,
p+: +ve, massive, in nucleus
Nucleus is small compared to size of atom

e– p+ n°
n° p+

Helium atom is
e– shown
 Background: basic structure
Previous slide was a single atom
Let’s look at a compound:

Cl Na

• Notice that the nuclei are far apart

• Only the outer regions come in close contact
• In other words, it’s the electrons that are important
in bond formation
1903s; Rutherford had proposed that electron is
negatively charge that fill the volume of the atom
(orbit).
◦ Argued: the speed of the movement and distance
from the nuclei. This 2 important information is
needed in order to explain the orbit movement.
Too fast: out of orbit; too slow: e- will attract to the
nuclei.
To overcome this problem, Neils Bohr (1913) come
out with new theory (Bohr Theory).
 Background
Rutherfords model (1903s) is in trouble: an “accelerated charge” should fall
into nucleus

• Bohr revised Rutherford’s model to explain the

existance of line spectra for elements…
 Bohr Model
➢ Bohr model assumed that a hydrogen atom consists of a central proton
about which an electron moves in a circular orbit.
Line spectra
❑A spectrum is produced when radiation from such
sources is separated into its component
wavelengths.
❑ Rainbow colors: containing light of all
wavelength (continuous spectrum)
❑A spectrum containing radiation of only specific
wavelength is call a line spectrum.
❑Line spectrum result from the release of photons
as electrons fall back to lower orbit
The basic clue to the electronic structures of atoms comes from the study
of the light emitted when atoms of the elements are excited, or energized.
To learn about this, however, you must first learn a little about light itself.
As we know energy can be transferred as light energy (important form of
energy in chemistry)
Because many chemical systems emit visible light as they react.

More properly called

electromagnetic energy
 The Wave Nature of Light:
Wavelength and Frequency
To understand the evidence that led Bohr to his conclusion we must
understand something about the nature of light…
✓ light is a type of EM energy and has wave properties.
✓Wavelength ( ) and frequency ( ) are related by :
 x  = c = 3.00 x 108 m/s
✓Frequency (or wavelength) determines the type of radiation.
 c
=


y = the max. height of the wave above centre line or the max. depth

c below

=
λ = wavelength; the distance between the tops of the two successive crest
(or the bottom of two troughs); unit in meter
ν= frequency; the number of crest or troughs that pass through a given


point per unit of time; unit hertz (Hz)
c = the speed of electromagnetic radiation in a vacuum
(speed of light) 3.00 X 108 ms-1
Calculating frequency from wavelength
1) What is the frequency in hertz of yellow light that has a wavelength
of 625 nm?
Solution:
➢ ν = 3.00 X 108 ms-1 / 625 X 10-9 m
= 4.80 X 1014 s-1
= 4.80 X 1014 Hz

2) What is the frequency in hertz of blue light that has a wavelength of

450 nm?
Solution:
➢ ν = 3.00 X 108 ms-1 / 450 X 10-9 m
= 6.67 X 1014 s-1
= 6.67 X 1014 Hz
 EXAMPLE:
1) In a grocery store, a scanner uses a laser with the frequency of
4.62 x 1014 to scan the bar code on a power drink. The store pipes
in music from an FM station with a frequency of 286 cm.

a) What is the frequency of the FM station?

b) What is the wavelength of the laser in nm?
 The electromagnetic spectrum

❖
Relation Between Color and
Wavelength
❖Electromagnetic radiation comes in a broad range of frequencies
called the electromagnetic spectrum.

❖ Most of the time, you are bombarded with electromagnetic

radiations from all portion of the EM spectrum.
➢ Radio & TV signals pass through you
➢ You feel infrared radiation when you sense the warmth of a
radiator
➢ X rays and gamma rays fall on you from space
➢Light from a lamp reflects into your eyes from the page you’re
reading
✓ our eyes are able to sense only a very narrow band of wavelength ranging from about 400 nm to 700 nm
✓ this band is called the visible spectrum
The energy of EM radiation

In 1900 a German physicist named Max Planck (1858 –

1974) launched one of the greatest upheavals in the
history of science when he proposed that
electromagnetic radiation is emitted only in tiny packets
or quanta of energy that were later called photons.

Planck proposed, and Albert Einstein (1879-2955)

confirmed, that the energy of a photon of
electromagnetic radiation is proportional to its
frequency.
Planck’s Constant
Transfer of energy is quantized, and can only
occur in discrete units, called quanta.
hc
E = h =

E = change in energy, in J
h = Planck’s constant, 6.626  10−34 J.s
ν = frequency, in s−1
 = wavelength, in m
E = hv
c
 =

hc
E=

Example 2
Calculate the quantum energy of
a) orange lights that has frequency of 4.92 X 1014 s-1
b) blue lights with frequency of 6.67 x 1014 s-1
Solution:
a) ∆𝐸 = ℎ𝑣 = (6.63 𝑥 10 − 34𝐽𝑠)(4.92 X 1014 s-1) = 3.26 x10-19 J
b) ∆𝐸 = ℎ𝑣 = (6.63 𝑥 10 − 34𝐽𝑠)(6.67 X 1014 s-1) = 4.42 x10-19 J
Example 2
Sodium vapor lamps are commonly used to illuminate highways
because their intense yellow-orange emissions at 589 nm.
a) Calculate the energy, in joules, of one photon of this light.
b) Calculate the energy, in kilojoules, of one mole of such photons.
 Quantum Numbers
According to Heisenberg’s Uncertainty
Principle, it is not possible to give the exact
position of an electron and its energy at
the same time.
But the probability of finding an electron
in an orbital of given energy can be
determined.
The Three Physicists
Louie de Broglie
Erwin Schrodinger
Werner Karl Heisenberg

Quantum Mechanical Model

 An orbital:

The • describes a specific distribution of

Quantum electron density in space
• has a characteristic energy
Mechanical • has a characteristic shape
Model • is described by three quantum numbers:
n, l, ml
• can hold a maximum of 2 electrons

Note: A fourth quantum number

(ms) is needed to describe each
electron in an orbital
 Principal Quantum
Number, n

The 4 Azimuthal Quantum

Quantum Number, l
Numbers Magnetic Quantum
Number, ml
Spin Quantum Number,
ms
 The quantum number, n is called the principal
quantum number.

1. The All orbitals that have the same value of n are said
to be in the same shell.
Principle
Range: n = 1 to n = ∞
Quantum
Number, n n=1 first shell

n=2 second shell

Sometimes identified by letters (with no significant

reason) beginning with K for the first shell.
• n is related to the size of the electron wave
(how far the wave effectively extend from the
nucleus).
• n; electron’s average distance from the
nucleus.
• n also related to the energy of the orbital.
• n; Eorbital

• Bohr theory failed for atom other than

hydrogen b’coz when the atom has more than
one electron, different orbitals with the same
value of n can have different energy.
 2. The Secondary Quantum Number, l;
sublevels (s, p, d, f)

Also called the

l, divides the shells into
azimuthal quantum The value of n
smaller group of determines which
number / also know as
orbitals called
angular momentum values of l are allowed.
subshells.
quantum number

Example:
• n = 1; (n-1) = 0, so the only
Range: l = 0 to l = (n-1) value of l that’s allowed is
zero.
 Azimuthal Quantum Number
l Subshell Total orbitals Orbital
(2l + 1) Shape
0 sharp - s 1 spherical

1 principal - p 3 dumbbell-
shaped
2 diffused - d 5 cloverleaf

3 fundamental - f 7 too
complex
 value of n value of l Kind of Subshell
1 0 1s
2 0, 1 2s, 2p
3 0, 1, 2 3s, 3p, 3d
4 0, 1, 2, 3 4s, 4p, 4d, 4f
n 0, 1, 2, … (n – 1)

l 0 1 2 3

Sign of orbital s p d f

Total orbitals 1 3 5 7
2l + 1
 Summary: p orbitals and d orbitals
p orbitals look like
a dumbell with 3
orientations: px,
py, pz (“p sub z”).
Four of the d orbitals resemble two dumbells in a
clover shape. The last d orbital resembles a p
orbital with a donut wrapped around the middle.
 The Quantum Mechanical Model

s-orbital:

◦ spherical probability region 1s

◦ found in all shells of an atom 2s

◦ the size of the s-orbital increases with increasing n

◦ as n increases an electron 3s
has a greater probability of being found farther
from the nucleus
 The Quantum Mechanical Model

• p-orbital
– Three p orbitals in
all shells when n > 2
– Figure 8 or dumbbell
shaped
• same size and
energy within
same shell
• different spatial
orientation
 The Quantum Mechanical Model

• d-orbitals
– five d orbitals are
present in each shell
where n > 3
– same energy within
same shell
– different shapes
– Different orientation
in space
 The Quantum Mechanical Model

• f-orbitals

– When n > 4, there are

seven equivalent f
orbitals in each shell.

– Complicated shapes
 3. Magnetic Quantum Number, ml

➢ describes the
orientation in
space of the
orbital
➢ integral values
between l and -l
• If l = 1, then
ml = 1, 0, -1

ml = -1 ml = 0 ml = 1
 4. Spin Quantum Number, ms

• The first three quantum numbers (n, l, ml) describe

an individual orbital.

• A fourth quantum number is used to describe each

electron found in an orbital.

• Electron spin quantum number (ms)

➢ms = + 1/2 ( ) or

➢ms = -1/2 ( )
value value of l Kind of Subshell Total Maximum
of (no. of subshells) Orbitals electron
N (2i + 1) population of a
(no of shell
shell) 2n2

1 0 1s 1 2

2 0, 1 2s, 2p 4 8

3 0, 1, 2 3s, 3p, 3d 9 18

4 0, 1, 2, 3 4s, 4p, 4d, 4f 16 32

n 0, 1, 2, … (n – 1)
 Orbital diagrams help visualize which
orbitals the electrons in an atom are.

The Basics of Orbital Diagrams:

• There are different types of orbitals, that all

ORBITAL have different energy levels. These orbitals are
filled with electrons (the amount of electrons

DIAGRAMS depends on which element you are looking at).

• S orbitals make up 1 box, and contain a max
of 2 electrons
• P orbitals make up 3 boxes, and contain a max
of 6 electrons total (2 in each box)
• D orbitals make up 5 boxes, and contain a
max of 10 electrons (2 in each box)
• F orbitals make up 7 boxes, and contain a max
of 14 electrons (2 in each box)
CHEAT SHEET
 Orbital Diagrams D orbitals make up 5 boxes,
and contain a max of 10
electrons (2 in each box)
4p
n=4
3d
4s
P orbitals make up 3 boxes,
n=3 3p
and contain a max of 6
3s electrons total (2 in each
Energy n=2 box)
2p
2s
n=1 S orbitals make up 1 box, and
contain a max of 2 electrons
1s
 Orbital Diagrams
3s 3p 3d
n=3

subshell
3s 3p 3d
n=3

shell

3s 3p 3d
n=3
 The collection of orbitals
with the same value of n
is called an electron shell.
The • All orbitals that have n = 3 are
Quantum in the third shell.

Mechanical The set of orbitals that

have the same n and l
Model values is called a subshell.
• All orbitals with n = 3 and l = 2
are called the 3d orbitals and
are located in the 3d subshell.
 For a hydrogen atom or an ion
containing only one electron,
the energy of a subshell
depends only on its principal
quantum number.
Orbital • i.e. 3s, 3p, and 3d subshells all have
the same energy
Diagrams
This is not true for atoms or
ions that have more than one
electron.
 • In atoms with more than one
electron, electron-electron
repulsion causes different
subshells within the same
Orbital shell to have different
energies.
Diagrams – Within the same shell: s
<p<d<f

– Note that there is overlap

in the subshell energies:
• 4s is lower energy than
3d
 Aufbau Principle: lower energy
orbitals fill before higher
How to Write energy orbitals.
Electron Hund's Rule: one electron goes
Configuration into each until all of them are
for an half full before pairing up.
Element Pauli Exclusion Principle: no
two electrons can be identified
by the same set of quantum
numbers (i.e. must have
different spins).
 • The Aufbau Principle states that lower energy
orbitals fill before higher energy orbitals. For
example, the orbitals in the n=1, energy level will fill
up before the orbitals in the n=2 energy level.

• Hund's Rule states that if 2 or more degenerate

(i.e. same energy) orbitals are available, one
electron goes into each until all of them are half full
before pairing up. You may have heard this one in
relation to the analogy of filling seats in a bus;
everyone finds their own seat, and only when all
the seats are half full do they start sitting together?
EXPLAINATION
• The Pauli Exclusion Principle states that no two
electrons can be identified by the same set of
quantum numbers. This is actually why we have the
spin quantum number, ms, to ensure that two
electrons within the same orbital have unique sets
of quantum numbers. You may also hear this in the
form that the two electrons in an orbital must have
opposite spins, which essentially means the same
thing.
 No two electrons in an atom can have
the same set of four quantum numbers
n, l, ml, and ms.
Pauli
In order to put more than one electron
Exclusion in an orbital, electrons must have
different values of ms (↑ or ↓).
Principle:
Maximum of 2 electrons per orbital

Two electrons can occupy the same

orbital only if their spins are paired
Aufbau Principle
- Electrons are
placed in the
lowest energy • Diagonal Diagram:
orbital
available • a guide used to
determine the relative
energies of subshells in
multi-electron atoms
 Electron configuration
• The way electrons are distributed among
various orbitals of an atom
• Unpaired electrons: electrons that are alone
in an orbital; not accompanied by another
electron of opposite spin.
• Use Hund’s Rule, The Pauli Exclusion & Aufbau
Principle
• E.g.: Helium. (No. of e-: 2e)
He : 1s2
1s
Electron
Configuration
 Example: Chromium
(Element 24), Copper
(Element 29)

Electron Consequence of the

Configuration closeness of the 3d and
Exceptions 4s orbital energies.

These elements are more

stable.
 EXAMPLE
What is the orbital diagram for Sulfur?

1) Look at the periodic table to see how many electrons sulfur

has
▪ In this case, sulfur has 16 electrons that need to be placed
into orbitals
2) Looking at our cheat sheet, draw the orbitals one at a time,
adding electrons as you go, until you reach a total of 16
electrons
Exercise
• Draw the orbital diagram for the electron
configuration of oxygen, atomic no 8. How
many unpaired electrons does oxygen posses?
• Write the electron configuration for
phosphorus, element 15. How many unpaired
electrons does a phosphorus atom posses?
• Write the electron configuration for Cr
(Atomic No: 24)