The Electronic Structure of

Atoms
Chapter 7

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Can we see the atoms?

https://imgur.com/gallery/tvQ4V

A boy and his atom…

∼70000 PT atoms 2
CO molecules by IBM https://youtu.be/oSCX78-8-q0 https://youtu.be/yqLlgIaz1L0

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 Classical physics
vs Quantum mechanics
• Classical physics (Newton’s Laws) is used to understand
the behavior of big particles known as macro-particles
(rocks, satellites, cars, animals, etc.).

Example:
Speed of a piece of stone can be calculated from:
!
𝑣=" 𝑑 = 𝑑𝑖𝑠𝑡𝑎𝑛𝑐𝑒 𝑡𝑟𝑎𝑣𝑒𝑙𝑙𝑒𝑑, 𝑡 = 𝑡𝑖𝑚e elapsed
The distance travelled can be estimated by using the same
equation if the speed and elapsed time are known.

• However, the same equation for speed fails in

calculation of the distance at a given time for very
small particles likle electrons, protons, atoms etc.,
• In general, equations of classical physics for speed,
acceleration, momentum etc., can not be used for
electrons or atoms (micro-particles)

• Then, a new set of equations to explain the behavior

of micro-particles.
• These equations are derived with a totally new
mathematical approach known as
QUANTUM MECHANICS.

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 • Equations derived from the rules of quantum
mechanics explain the behavior of microparticles.
• As an example, this equation calculates the probability
of finding an electron at a specific distance (r) and
angle from the nucleus.

• As you see in this example, equations in quantum

mechanics are very complicated and the details are
out of the scope of this course.
• However, please note that there are some variables
like n, l, and m etc., in the equation. These variables
themselves provide very useful information like the
energy, shape, orientation and magnetic properties of
an atom’s electrons.
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• In more generalized quantum mechanics equations

there are two m values: ml and ms.
• All together, n, l, ml and ms are known as “quantum
numbers”.
• We will learn the most basic properties of an atom by
having a quick look at the values of these quantum
numbers.

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 • The basis of quantum mechanics is that the energy of
a particle, such as an electron, is quantized. This
means that energy levels are discrete, jumping from
one value to another instead of changing smoothly or
linearly.

• Therefore, quantum numbers (n, l, ml and ms) are not

continuous; they jump from one value to another,
resulting in the emission or absorption of energy
packets with discrete values called photons.

Research on the interaction of light with atoms, combined

with advancements in high-tech computer systems, has led
to the development of quantum mechanical equations for
atoms. Line Emission Spectrum of Hydrogen Atoms

Line Emission Spectrum of atoms of

some other elements

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 Quantum numbers (n, l, ml, ms)

• Every electron of each atom has a set of four quantum

numbers.
• For example the two electrons of He has the following
quantum numbers:

n l ml ms
1st electron 1 0 0 +1/2
2nd Electron 1 0 0 -1/2

• No two electrons of the same atom has the same set

of n, l, ml and ms

• Assigning numbers to n, l, ml and ms follows specific rules.

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n : Principal quantum number

n = 1, 2, 3, 4, …. (minimum n is 1, maximum is ∞)

• n gives information about the distance of an electron from nucleus

• Average distance increases as n increases

n=3
n=2
n=1

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 Exercise 5
Which n values are invalid? Why?

a) n = 3

b) n = 0

c) n = -2

d) n = 5005

e) n = 3.75

f) n = ½

g) n = 1
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Ans: b, c, e, f

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Angular momentum quantum number l

for a given value of n, l = 0, 1, 2, 3, … n-1

n = 1, l = 0
It is common in chemistry to represent the
n = 2, l = 0 or 1 value of l with a letter.
n = 3, l = 0, 1, or 2 l=0 s orbital
l=1 p orbital
l=2 d orbital
l=3 f orbital
l gives information about the shape of an orbital.

(Orbital: volume of space in which an e- moves around nucleus)

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 Exercise 6
Which l values are invalid for an electron with n = 2? Why?

a) l = 1

b) l = 0

c) l = 3

d) l = 0.8

e) l = -1

f) l = -2

g) l = +∞
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Ans: c, d, e, f, g

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Exercise 7
Which orbitals are impossible (invalid) for an electron? Why?

a) 3s

b) 1p

c) 2s

d) 1s

e) 3f

f) 2p

g) 4f

h) 5d

i) 2b
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Ans: b, e, i

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 magnetic quantum number ml

for a given value of l

ml = -l, …., 0, …. +l

if l = 1 (p orbital), ml = -1, 0, or 1
if l = 2 (d orbital), ml = -2, -1, 0, 1, or 2

ml gives information about orientation of the orbital in space

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Exercise 8

Which ml values are invalid for an electron with l = 2 ? Why?

a) ml = 1

b) ml = 0

c) ml = 3

d) ml = 0.8

e) ml = -1

f) ml = -2

g) ml = +∞
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Ans: c, d, g

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 quantum numbers: (n, l, ml, ms)

spin quantum number ms

ms = +½ or -½

ms = +½ ms = -½

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Exercise 9
Which ms values are invalid for an electron? Why?

a) ms = 1/2

b) ms = 0

c) ms = 3/2

d) ms = -1/2

e) ms = 1

f) ms = 0.5 !!!

g) ms = 0.75

f: 0.5=1/2 but we always show ms as ½ or -1/2 not not 0.5 or -0.5

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Ans: b, c, e, f, g

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 19

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Where 90% of the

e- density is found
for the 1s orbital

Electron cloud of 1s orbital

1s orbital

Orbital: Volume of space in which the probability of finding

an electron is 90%
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 l = 0 (s orbitals)

l = 1 (p orbitals)

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l = 2 (d orbitals)

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Example 7.6

List the values of n, ℓ, and mℓ for orbitals in the 4d subshell.

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Example 7.6
Strategy What are the relationships among n, ℓ, and mℓ?
What do “4” and “d” represent in 4d?

Solution As we saw earlier, the number given in the

designation of the subshell is the principal quantum number, so
in this case n = 4. The letter designates the type of orbital.
Because we are dealing with d orbitals, ℓ = 2. The values of mℓ
can vary from −ℓ to ℓ. Therefore, mℓ can be −2, −1, 0, 1, or 2.

Check The values of n and ℓ are fixed for 4d, but mℓ can have
any one of the five values, which correspond to the five d
orbitals.

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 ml = -1, 0, or 1 3 orientations is space

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ml = -2, -1, 0, 1, or 2 5 orientations is space

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Example 7.7

What is the total number of orbitals associated with the principal

quantum number n = 3?

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Example 7.7
Strategy To calculate the total number of orbitals for a given n
value, we need to first write the possible values of ℓ. We then
determine how many mℓ values are associated with each value
of ℓ. The total number of orbitals is equal to the sum of all the
mℓ values.

Solution For n = 3, the possible values of ℓ are 0, 1, and 2.

Thus, there is one 3s orbital (n = 3, ℓ = 0, and mℓ = 0); there are
three 3p orbitals (n = 3, ℓ = 1, and mℓ = −1, 0, 1); there are five
3d orbitals (n = 3, ℓ = 2, and mℓ = −2, −1, 0, 1, 2). The total
number of orbitals is 1 + 3 + 5 = 9.

Check The total number of orbitals for a given value of n is n2.

So here we have 32 = 9. Can you prove the validity of this
relationship?

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 Arrangement of electrons in an atom:
“Electron Configuration”
• Each electron in an atom is placed in an orbital
• The placement order is from lowest-energy-orbital to
highest-energy orbital. (1s is the lowest energy orbital).
• Each orbital hosts one or a maximum of two electrons
• The placement order of electrons into orbitals is done in
such a way that no two electrons in an atom can have
the same four quantum numbers.
(Pauli exclusion principle)
• Orbitals having the same n and l are said to be in the
same subshell.
e.g., all electrons in three p-orbitals in 2p subshell have
n=2, l=1
• Electrons in an orbital have the same n, l, and ml
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Electron configuration shows how the electrons are

distributed among the various atomic orbitals in an
atom.
number of electrons
in the orbital or subshell
1s1
principal quantum angular momentum
number n quantum number l

Orbital diagram

H
1s1
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 Energy of orbitals in a single electron atom
Energy only depends on principal quantum number n

n=3

n=2

n=1

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Energy of orbitals in a multi-electron atom

Energy depends on n and l

n=3 l = 2

n=3 l = 1
n=3 l = 0

n=2 l = 1
n=2 l = 0

n=1 l = 0
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 “Fill up” electrons in lowest energy orbitals (Aufbau principle)

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The most stable arrangement of electrons in

subshells is the one with the greatest number of
parallel spins (Hund’s rule).

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 Order of orbitals (filling) in multi-electron atom

1s < 2s < 2p < 3s < 3p < 4s < 3d < 4p < 5s < 4d < 5p < 6s
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Example 7.8

Write the four quantum numbers for an electron in a 3p orbital.

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Example 7.8
Strategy
What do the “3” and “p” designate in 3p?

How many orbitals (values of mℓ) are there in a 3p subshell?

What are the possible values of electron spin quantum

number?

Solution To start with, we know that the principal quantum

number n is 3 and the angular momentum quantum number ℓ
must be 1 (because we are dealing with a p orbital). For ℓ = 1,
there are three values of mℓ given by −1, 0, and 1. Because the
electron spin quantum number ms can be either +½ or −½, we
conclude that there are six possible ways to designate the
electron using the (n, ℓ , mℓ, ms) notation.

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Example 7.8
These are:

Check In these six designations we see that the values of n

and ℓ are constant, but the values of mℓ and ms can vary.

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 Exercise 16
Write the electron configuration of selenium (Se).

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Ans: Se (34 e): 1s2 2s2 2p6 3s2 3p6 4s2 3d10 4p4

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Paramagnetic Diamagnetic
unpaired electrons all electrons paired

2p 2p 40

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Example 7.9

What is the maximum number of electrons that can be present

in the principal level for which n = 3?

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Example 7.9
Strategy We are given the principal quantum number (n) so
we can determine all the possible values of the angular
momentum quantum number (ℓ). The preceding rule shows
that the number of orbitals for each value of ℓ is (2 ℓ + 1). Thus,
we can determine the total number of orbitals. How many
electrons can each orbital accommodate?

Solution When n = 3, ℓ = 0, 1, and 2. The number of orbitals

for each value of ℓ is given by

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Example 7.9

The total number of orbitals is nine. Because each orbital can

accommodate two electrons, the maximum number of electrons
that can reside in the orbitals is 2 × 9, or 18.

Check If we use the formula (n2) in Example 7.7, we find that

the total number of orbitals is 32 and the total number of
electrons is 2(32) or 18. In general, the number of
electrons in a given principal energy level n is 2n2.

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Example 7.10

An oxygen atom has a total of eight electrons. Write the four

quantum numbers for each of the eight electrons in the ground
state.

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Example 7.10
Strategy
We start with n = 1 and proceed to fill orbitals in the order
shown in Figure 7.21.

For each value of n we determine the possible values of ℓ.

For each value of ℓ, we assign the possible values of mℓ.

We can place electrons in the orbitals according to the Pauli

exclusion principle and Hund’s rule.

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Example 7.10
Solution
We start with n = 1, so ℓ = 0, a subshell corresponding to the 1s
orbital. This orbital can accommodate a total of two electrons.
Next, n = 2, and / may be either 0 or 1. The ℓ = 0 subshell
contains one 2s orbital, which can accommodate two electrons.
The remaining four electrons are placed in the ℓ = 1 subshell,
which contains three 2p orbitals. The orbital diagram is

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Example 7.10
The results are summarized in the following table:

Of course, the placement of the eighth electron in the orbital

labeled mℓ = 1 is completely arbitrary. It would be equally
correct to assign it to mℓ = 0 or mℓ = −1.

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Exercise 19
What is the maximum number of electrons that can be present in the
principal level for which n = 4?

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Ans: 32

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 Exercise 23
A fluorine atom has a total of nine electrons.
a) Write the electron configuration.
b) Write the four quantum numbers for the electrons in 2p.

2, 1, 0, -1/2
2, 1, 0, +1/2
2, 1, -1, -1/2
2, 1, -1, +1/2
d) n, l, ml ms
c) Paramagnetic
(↿⇂) (↿⇂) (↿⇂)(↿⇂)(↿ )
b) 1s2 2s2 2p5 xxxx
a) 1s2 2s2 2p5
Ans:

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 Outermost subshell being filled with electrons

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What is the shape of an atom?

It is the overall shape obtained by placing all the

orbitals of an atom's electrons around the nucleus
in a concentric arrangement.
See the simulations in the following links:
Electron Orbital Simulator by PatAle:
http://electronorbitalsimulator.com

Orbitals by 3DhubPlayer:
https://www.youtube.com/watch?v=4WR8Qvsv70s

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 Here are some examples to the shapes of some atoms
together with their crossectional views from “Orbitals”
simulation of 3DHubs:
He Atom (2 electrons): 1s2

Crossectional views

At a moment At another moment

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Here are some examples to the shapes of some atoms

together with their crossectional views from “Orbitals”
simulation of 3DHubs:
Be Atom (4 electrons): 1s22s2
Crossectional views

At a moment At another moment

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 Here are some examples to the shapes of some atoms
together with their crossectional views from “Orbitals”
simulation of 3DHubs:

Ne Atom (10 electrons) : 1s22s22p6

Crossectional view

At a moment

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Here are some examples to the shapes of some atoms

together with their crossectional views from “Orbitals”
simulation of 3DHubs:

Fe Atom (26 electrons) : 1s22s22p63s26p64s23d6

Crossectional view

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 Periodic Table of Elements

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