The Electronic Structure of

Atoms
Chapter 7

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Copyright © The McGraw-Hill Companies, Inc. Permission required for reproduction or display.

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 for macro-particles
(rocks, satellites, cars, animals etc.,). It fails to explain the
behavior of micro-particles (atoms, electrons, molecules,
ions, protons etc.,)

• Quantum Mechanics is used to understand micro-

particles.

• To understand the quantum mechanics, hence, the behavior

of micro-particles, we must understand the nature of light
and waves first.
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Theories regarding the structure of an atom are based on

studies involving the light emitted or absorbed by atoms

Line Emission Spectrum of Hydrogen Atoms

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 Line Emission Spectrum of each element is different
(fingerprint)

Each line in these spectra is related to the jump of an electron from one
energy state to another energy state.

Light is emitted if an electron jumps from a high energy state to a low energy
state.

Energy of electrons is not continues. An electron can only have specific

(quantized) energy values 5

Simplest model of an atom

• e- can only have specific

(quantized) energy values
• light is emitted as e- moves
from one energy level to a
lower energy level
• Each energy level is shown
with an integer number n

n (principal quantum number) = 1,2,3,…

In reality each electron of an atom has 4 different

energy states (four different quantum numbers:
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n, l, ml, ms
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 An atom’s electronic structure (organization of an
atom’s electrons around nucleus) can be
understood by using an equation in which we have
these four quantum numbers: n, l, ml, ms
This equation is called Shrödinger’s wave equation.
It is too complicated.
We will just see the outputs of this equation as a
function of n, l, ml, ms to understand the atom.

quantum numbers (n, l, ml, ms)

principal quantum number n

n = 1, 2, 3, 4, ….

distance of e- from the nucleus

n=1 n=2 n=3

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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

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

angular momentum quantum number l

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

l=0 s orbital
n = 1, l = 0
l=1 p orbital
n = 2, l = 0 or 1
l=2 d orbital
n = 3, l = 0, 1, or 2
l=3 f orbital
Shape of the “volume” of space that the e- occupies
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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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 quantum numbers: (n, l, ml, ms)

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

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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 17

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Where 90% of the

e- density is found
for the 1s orbital

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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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 Organization of electrons in an atom:
“Electron Configuration” and “Orbital
Diagrams”
This is based on Shrödinger’s equation with quantum
numbers: (n, l, ml, ms)

Pauli exclusion principle - no two electrons in an atom

can have the same four quantum numbers.

Each seat is uniquely identified (E, R12, S8).

Each seat can hold only one individual at a
time.
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Shell – electrons with the same value of n

Subshell – electrons with the same values of n and l

Orbital – electrons with the same values of n, l, and ml

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 Electron configuration is 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

1
En = -RH ( )
n2

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 39

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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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Example 7.11
Write the ground-state electron configurations for

(a) sulfur (S)

(b) palladium (Pd), which is diamagnetic.

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Example 7.11
(a) Strategy How many electrons are in the S (Z = 16) atom?
We start with n = 1 and proceed to fill orbitals in the order
shown in Figure 7.21. 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
and then write the electron configuration. The task is
simplified if we use the noble-gas core preceding S for the
inner electrons.

Solution Sulfur has 16 electrons. The noble gas core in

this case is [Ne]. (Ne is the noble gas in the period
preceding sulfur.) [Ne] represents 1s22s22p6. This leaves
us 6 electrons to fill the 3s subshell and partially fill the 3p
subshell. Thus, the electron configuration of S is
1s22s22p63s23p4 or [Ne]3s23p4 .

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Example 7.11
(b) Strategy We use the same approach as that in (a). What
does it mean to say that Pd is a diamagnetic element?

Solution Palladium has 46 electrons. The noble-gas core in

this case is [Kr]. (Kr is the noble gas in the period preceding
palladium.) [Kr] represents

1s22s22p63s23p64s23d104p6

The remaining 10 electrons are distributed among the 4d

and 5s orbitals. The three choices are (1) 4d10, (2) 4d95s1,
and (3) 4d85s2.

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Example 7.11
Because palladium is diamagnetic, all the electrons are paired
and its electron configuration must be

1s22s22p63s23p64s23d104p64d10

or simply [Kr]4d10 . The configurations in (2) and (3) both

represent paramagnetic elements.

Check To confirm the answer, write the orbital diagrams for (1),
(2), and (3).

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 Exception of aufbau principle for 29Cu
and 24Cr.
distribution of electrons in half-filled or completely-filled
electronic configurations are symmetrical and occupies
more stability. Therefore, electronic configurations of
chromium and copper are ;

24Cr= 1s² 2s² 2p⁶ 3s²3p6 4s¹ 3d⁵

29Cu =1s² 2s² 2p⁶ 3s² 3p⁶ 4s¹ 3d¹⁰

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Electron Configurations of Cations and Anions

Of Representative Elements

Na [Ne]3s1 Na+ [Ne]

Atoms lose electrons so that
Ca [Ar]4s2 Ca2+ [Ar] cation has a noble-gas outer
electron configuration.
Al [Ne]3s23p1 Al3+ [Ne]

H 1s1 H- 1s2 or [He]

Atoms gain electrons
so that anion has a F 1s22s22p5 F- 1s22s22p6 or [Ne]
noble-gas outer
O 1s22s22p4 O2- 1s22s22p6 or [Ne]
electron configuration.
N 1s22s22p3 N3- 1s22s22p6 or [Ne]
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 Cations and Anions Of Representative Elements
+1
+2

+3

-3
-2
-1
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Isoelectronic: have the same number of electrons, and hence the same ground-state
electron configuration

Na+: [Ne] Al3+: [Ne] F-: 1s22s22p6 or [Ne]

O2-: 1s22s22p6 or [Ne] N3-: 1s22s22p6 or [Ne]

Na+, Al3+, F-, O2-, and N3- are all isoelectronic with Ne

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 Electron Configurations of Cations of Transition Metals

When a cation is formed from an atom of a transition metal,

electrons are always removed first from the ns orbital and
then from the (n – 1)d orbitals.

Fe: [Ar]4s23d6 Mn: [Ar]4s23d5

Fe2+: [Ar]4s03d6 or [Ar]3d6 Mn2+: [Ar]4s03d5 or [Ar]3d5
Fe3+: [Ar]4s03d5 or [Ar]3d5

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