01

NOTE
C H E M I S T R Y

ATOMIC STRUCTURE
ELECTRONIC CONFIGURATION

What you already know

• Dalton’s atomic theory • Heisenberg’s uncertainty principle

• Discovery of subatomic particles • Quantum numbers
• Bohr’s atomic model • Orbits & orbitals
• Hydrogen spectra

What you will learn

• Subshell notation • Pauli’s exclusion principle

• Energy levels of orbitals • Hund’s rule of maximum multiplicity
• Aufbau rule • Diamagnetic vs paramagnetic species
• Simplified electronic configuration • Exceptional configurations
• Spin quantum number

Let us revise

Types of orbitals
• s-orbital: Spherical shape • p-orbital: Dumb-bell shape
• d-orbital: Double dumb-bell shape • f-orbital: Leaf-like shape

s-orbital
z

Fig. 1: Spherical shaped s-orbital

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p-orbital z z z
y y

x x x

px pz py
Fig. 2: Dumb-bell shaped p-orbitals

z z z
d-orbital
y

x y y
x x

dxy dxz dyz

z z

y y
x

dx 2 - y 2 dz 2
Fig. 3: Double Dumb-bell shaped d-orbitals

f-orbitals z z z

x x y x y
y

fz3 fxz2 fyz2

z z z z

x y x
y x x y
y

fxyz fz(x 2 - y 2 ) fx(x 2 - 3y 2 ) fy(3x 2 - y 2 )

Fig. 4: Leaf like shape of f-orbitals

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MAIN BOARDS
Quantum Numbers

Each electron in an atom can be described by a unique set (set of four) of numbers. These
numbers are called quantum numbers. Following are the four quantum numbers.
Principal quantum number (n): It describes the size of the electron wave and the total energy of
the electron. It has integral values 1, 2, 3, 4, ...., etc., and is denoted by K, L, M, N,...., etc.
Azimuthal quantum number (l): It describes the shape of an electron cloud and the number of
subshells in a shell. The value of l depends on n and ranges from 0 to (n − 1).
Magnetic quantum number (m): It describes the orientations of orbitals with respect to the
standard set of coordinate axes. The value of m ranges between the interval - l to + l. The value of
m indirectly depends on n since the value of l depends on n.
Spin quantum number (s): It describes the spin of the electron. It can have values + 1 or – 1 . They
2 2
are normally represented by two arrows, up arrow and down arrow

Azimuthal Quantum Number

Value of l Subshell Description

0 s Sharp

1 p Principal

2 d Diffused

3 f Fundamental

In a Nutshell

• The number of subshells in a shell = n

• The number of orbitals in a shell = n 2
• The maximum number of electrons in a shell = 2n 2
• The number of orbitals in a subshell = 2l + 1
• The maximum number of electrons in a subshell = 2(2l + 1)
h
• Orbital angular momentum = √( l (l + 1))
2π

Subshell Notation

We need quantum numbers to specify the position of an electron in the atom. Out of four quantum
numbers, the principal quantum number (n), the azimuthal quantum number (l), and the magnetic
quantum number (ml) define the size, energy, shape and orientation of the orbital. The fourth
quantum number, i.e., the spin quantum number (s) accounts for the spin motion of the electron.
Physicists and chemists use a standard notation to indicate the electron configurations of atoms
and molecules.

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For example: For Neon 10Ne - 1s2 2s2 2p6, the notation consists of a sequence of atomic subshell
labels with the number of electrons assigned to each subshell placed as a superscript.
Example: If the p-orbitals of the second shell contain five electrons, then the notation follows the
fashion as shown below.
Number of electrons in p subshell = 5

Subshell p (l = 1)

The subshell 'p' belongs to second shell.

i,e., n = 2 or Principal Quantum Number = 2
From the mathematical conclusions of quantum numbers,

Subshell Value of l Number of orbitals (2l + 1)

s 0 1

p 1 3

d 2 5

f 3 7

g 4 9

MAIN BOARDS
Rules for filling electrons in orbitals

The following are the rules that need to be followed while filling electrons in orbitals.
1. Pauli’s exclusion principle
2. Bohr-bury rule or (n + l) rule
3. Aufbau's principle
4. Hund’s rule for maximum multiplicity

MAIN BOARDS
Pauli’s Exclusion Principle
s2
No two electrons in an atom can have the same
set of all the four quantum numbers. This means p6
that only two electrons may exist in the same
orbital and these electrons must have opposite
d10
spin.

f14
The filling of electrons in subshells is shown in
given the Fig. 5. Fig. 5: Subshell-electron capacity

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MAIN BOARDS
Bohr-Bury Rule or (n + l) Rule

Energy levels of orbitals

The diagram representing energy levels of orbitals is known as the ‘energy level diagram’. These
differences in the energy of orbitals arise due to the mutual interaction between positively charged
and negatively charged particles present in the atom. Based on the number of electrons present in
the atom, mutual interaction can be of two types, i.e., the attraction between a negatively charged
electron and positively charged nucleus, and secondly, the repulsion between negatively charged
particles.

Energy of orbitals

Mono-electronic system Poly-electronic system

Attraction Electron
Outer electrons

Inner
electrons Repulsion
Nucleus
Attraction

Fig. 6: Different interactions in atom

In mono-electronic systems like H, He+, Li2+, etc. 4s 4p 4d 4f

n=4
the energy is solely determined by the principal 3s 3p 3d
quantum number (n). Thus, the order looks like 1s n=3
< 2s = 2p < 3s = 3p = 3d < 4s = 4p = 4d = 4f < …
2s 2p
Energy

The subshells or the orbitals that have the same n=2

energy are said to be degenerate.
Example: 4s = 4p = 4d = 4f (degenerate subshells) 1s
& 3px = 3py = 3pz (degenerate orbitals) n=1
Fig. 7: Energy level diagram for
Bohr-Bury rule or (n + l) rule mono-electronic system
In a poly-electronic system, along with the nucleus-electron attractive forces, the electron-electron
repulsive forces also exist. The azimuthal quantum number (l) combines with the principal quantum
number (n) to decide the energy levels of the orbitals according to the Bohr-bury rule or the
(n + l) rule.
The Bohr-bury rule says that,
• The energy level follows the (n + l) rule in the ascending order.
• If two subshells have the same value of (n + l), then the subshell with the lower value of n has
lower energy and it should be filled first.

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Example:

Filling of 1s and 2s orbitals based on the Bohr-bury rule or the (n + l) rule

(n + l) = 1 + 0
1s
=1 Since, (n + l) value of 2s > 1s,
(n + l) = 2 + 0 1s will be filled before 2s.
2s
=2

Filling of 2p and 3s orbitals based on the Bohr-Bury rule or the (n + l) rule

2p (n + l) = 2 + 1
=3 Since, (n + l) value of 2p = 3s,
2p will be filled before 3s since its value of n is lower
(n + l) = 3 + 0
3s
=3

3d
The energy order of subshells in a poly-electronic
4s
atom follows the trend as, 1s < 2s < 2p < 3s < 3p < 4s
< 3d < 4p < 5s < 4d < 5p < 6s ... 3p
No subshell is degenerate in a poly-electronic system. 3s
However, degenerate orbitals do exist.
Energy

Example: 2p

3px = 3py = 3pz (Degenerate orbitals) 2s

Thus, the subshell energy levels of orbitals look like
1s
Fig. 8: Energy level diagram for
multi-electron system

MAIN BOARDS
Aufbau Rule

Aufbau is a German word that means ‘building up’.

The electrons are filled in various orbitals in order 1s
of their increasing energies, i.e., the orbital of 2s 2p
lowest energy is filled first. Electrons first occupy
the lowest energy orbital available to them and 3s 3p 3d
enter into higher energy orbitals only after the
lower energy orbitals are filled. 4s 4p 4d 4f
Starting from the top, the direction of the arrows 5s 5p 5d 5f
gives the order of filling of orbitals (from the top
right to the bottom left). The given order should 6s 6p 6d
be assumed to be a rough guide to the filling of
energy levels. In many cases, the orbitals are 7s 7p
similar in energy and small changes in the atomic 8s
structure may bring about a change in the order of
filling. Fig. 9: Order of filling of orbitals

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MAIN BOARDS
Hund’s Rule of Maximum Multiplicity

Total spin of an atom

The total spin of an atom can be calculated

by multiplying the total number of unpaired
N
electrons in an atom by + 1 or - 1 depending on
2 2
the direction of an electron. Paired electrons do 1s2 2s2 2p3
not contribute to the total spin.
In the given example, the nitrogen atom has three unpaired electrons in its 2p orbital pointing
in an upward direction. So, the total spin of the nitrogen atom is calculated by multiplying 3 with
1 3
+ resulting in a total spin of +
2 2

Hund’s rule of maximum multiplicity

This rule states that no electron pairing take place in the orbitals in a subshell until each orbital is
occupied by one electron with a parallel spin.
Spin multiplicity = 2S + 1, where S (spin value of the configuration) = ΣmS
1
Upward directed electron has mS = + and a downward directed electron has mS = - 1
2 2
Example: 16O8 ; 1s2 2s2 2p4
Spin multiplicity = 2S + 1
where
 1  1  1  1
S   Number of electrons with + 2 spin  × 2 +  Number of electrons with − 2 spin  × − 2 
    
  1  1 
S=  4 ×   + 4 ×  −  = 0 O
 2  2 
Spin multiplicity = 2S + 1 = ( 2 × 0 ) + 1 = 1 1s 2s 2p

  1  1 
S=  4 ×   + 4 ×  −  = 0
 2  2  O
Spin multiplicity = 2S + 1 = ( 2 × 0 ) + 1 = 1 1s 2s 2p
  1  1 
S = 5 ×   + 3 −   = 1
 2  2  O
Spin multiplicity = 2S + 1 = ( 2 × 1) + 1 = 3 1s 2s 2p

Exactly half-filled and fully filled orbitals are

p3
observed to be more stable, i.e., p3, p6, d5, d10, f7,
and f14 configuration are most stable.

p3

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Reasons for the stability of half-filled and fully filled orbitals are as follows:
• Relatively small shielding
• Larger exchange energy
• Smaller coulombic repulsion energy

MAIN BOARDS ADVANCED

Exchange energy

Energy levels of orbitals

1 2

Two or more electrons with the same spin tend to 4 exchanges by 3 exchanges by
exchange their positions and the energy released 1st electron 2nd electron 
due to this exchange is known as exchange energy.
The number of exchanges that can take place is 3 4
maximum when the subshell is either half-filled or
completely filled.
2 exchanges by 1 exchange by 4th
3rd electron electron
Fig. 10: Exchange between the
electrons of half-filled d-orbitals

MAIN BOARDS ADVANCED

Electronic Configuration

The electron configuration is the standard notation used to describe the electronic structure of an
atom.
Example: Electronic configuration of Iodine atom can be written as

53
I = 1s2 2s2 2p6 3s2 3p6 4s2 3d10 4p6 5s2 4d10 5p5

Steps for writing electronic configuration:

Step 1: A
 rrange the subshells in the ascending order of their energies following the (n + l) rule. If
there is a tie for the the value of (n + l), then the subshell with the smaller value of n has
lower energy.
Step 2: Lower energy subshells are filled prior to the higher energy subshells.
Step 3: Electron pairing starts in an orbital after every orbital of the subshell gets half-filled.
(Hund’s rule of maximum multiplicity)

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Writing electronic configuration of the given element

Write the electronic configuration and find the number of unpaired electrons as well as total
spin for the following atoms.
(a) 6C (b) 8O (c) 15P (d) 21Sc (e) 26Fe (f) 10Ne

Solution

(a) 6C → 1s2 2s2 2p2

12 Number of unpaired electrons = 2
6 Total spin = 2 or - 2
Carbon 2 2
1s2 2s2 2p2
(b) 8O → 1s2 2s2 2p4
16 Number of unpaired electrons = 2
8 Total spin = 2 or - 2
Oxygen 2 2
1s2 2s2 2p4

(c) 15P → 1s2 2s2 2p6 3s2 3p3

31 Number of unpaired electrons = 3
15 Total spin = 3 or - 3
Phosphorus 2 2
3s2 3p3
(d) 21Sc → 1s2 2s2 2p6 3s2 3p6 4s2 3d1
or [Ar] 4s2 3d1 or [Ar] 3d1 4s2 Number of unpaired electrons = 1
45
21 Total spin = 1 or - 1
Scandium 2 2
4s 2
3d 1

(e) 26Fe → 1s2 2s2 2p6 3s2 3p6 4s2 3d6

or [Ar] 4s2 3d6 or [Ar] 3d6 4s2 Number of unpaired electrons = 4
56
26 Total spin = 4 or - 4
Iron 2 2
4s2 3d6

(f) 10Ne → 1s2 2s2 2p6

20
Number of unpaired electrons = 0
10
Neon Total spin = 0
1s2 2s2 2p6

MAIN BOARDS
Simplified Electronic Configuration

The configuration of an atom can be written in a simplified or condensed form by taking the
configuration of noble gases as the core. Electrons in completely filled shells are known as core
electrons, and electrons that are added to the shell with the highest principal quantum number are
known as valence electrons.

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The configuration of inert gases representing the core is written as [He]2, [Ne]10, [Kr]36, [Xe]54,
and [Rn]86.

Example: The electronic configuration of the elements sodium and argon is

Na : 1s2 2s2 2p6 3s1 Ar : 1s2 2s2 2p6 3s2 3p6

Ne Ne
This can be simplified as: Na: [Ne] 3s1 and Ar: [Ne] 3s2 3p6

MAIN BOARDS
Spin Quantum Number

It describes the spin of the electron. It can have values + 1 or – 1 and signifies opposites spins of
2 2
the two electrons in an orbital.
eh
• Spin magnetic moment μs = √s (s + 1)
2πmc
• Spin Magnetic moment ( μs) = √n (n + 2)
(n = Number of unpaired electrons)
h
• Spin angular momentum = √n (n + 2)
2π

• Maximum spin of atom = 1 × number of unpaired electrons

2
Example

6
C → 1s2 2s2 2p2
12 Number of unpaired electrons = 2
6 2 2
Total spin = or -
Carbon 2 2
1s 2
2s 2
2p
2

BOARDS
Diamagnetic vs Paramagnetic Species

Diamagnetic species

If two electrons are paired together in an orbital, or their total spin is 0, they are diamagnetic
electrons. Atoms with all diamagnetic electrons are known as diamagnetic atoms.
Example

10
Ne → 1s2, 2s2, 2p6
20
Number of unpaired electrons = 0
10
Neon Total spin = 0
1s 2
2s 2
2p 6

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Paramagnetic species

If any of the electrons are unpaired in a species, then these species are known as paramagnetic
species.
Example
26
Fe → 1s2 2s2 2p6 3s2 3p6 4s2 3d6
or [Ar] 4s2 3d6 or [Ar] 3d6 4s2 Number of unpaired electrons = 4
56
26 Total spin = 4 or - 4
Iron 2 2
4s2 3d6

MAIN BOARDS
Exceptional Configuration: Cr and Cu

Why does chromium have the configuration 4s1 3d5 instead of 4s2 3d4?

Expected:
52
4s2 3d4
24
Chromlum
Actual:
4s1 3d5
• This is due to the fact that half-filled d5 configuration is more stable than d4 configuration.
• The exchange energy is higher in d5 configuration as compared to d4.
Why does copper have the configuration 4s1 3d10 instead of 4s2 3d9 ?

Expected: 63.55
4s 2
3d 9
29
Copper
Actual:
4s1 3d10
• This is due to the fact that fully-filled d10 configuration is more stable than d9 configuration.
• The exchange energy is higher in d10 configuration as compared to d9.

Summary sheet

• Types of orbitals
s-orbital: Spherical shape having azimuthal quantum number (l) = 0
p-orbital: Dumbbell shape having azimuthal quantum number (l) = 1
d-orbital: Double dumbbell shape having azimuthal quantum number (l) = 2
f-orbital: Leaf-like shape having azimuthal quantum number (l) = 3
• Each electron in an atom can be described by a unique set (set of four) of numbers. These
numbers are called quantum numbers. Following are the four quantum numbers.
Principal quantum number (n): It describes the size of the electron wave and the total energy
of the electron. It has integral values 1, 2, 3, 4, ...., etc., and is denoted by K, L, M, N,...., etc.

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Azimuthal quantum number (l): It describes the shape of an electron cloud and the number of
subshells in a shell. The value of l depends on n and ranges from 0 to (n − 1).
Magnetic quantum number (m): It describes the orientations of orbitals with respect to the
standard set of coordinate axes. The value of m depends on l. The value of m ranges between
the interval - l to + l.
1 1
Spin quantum number (s): It describes the spin of the electron. It can have values + 2 or – 2 .
They are normally represented by two arrows, up arrow and down arrow.
• Rules for writing electronic configuration
• Pauli’s exclusion principle
• Aufbau’s principle
• Hund’s rule for maximum multiplicity
• Pauli’s exclusion principle
No two electrons in an atom can have the same set of all the four quantum numbers, i.e., an
orbital cannot have more than two electrons. For a set of electrons in an orbital, three quantum
numbers (principal, azimuthal, and magnetic) at the most may be the same and the fourth must
be different, i.e., their spins must be in opposite directions.
• Aufbau’s principle
The electrons are filled in various orbitals in order of their increasing energies. An orbital of
lowest energy is filled first.
• Hund’s rule for maximum multiplicity
No electron pairing takes place in the orbitals in a subshell until each orbital is occupied by one
electron with a parallel spin.
• Exactly half-filled and fully filled orbitals are observed to be more stable, i.e., p3, p6, d5, d10, f 7,
and f 14 configuration are most stable.
• Reasons for stability of half-filled and fully filled electrons
• Relatively small shielding
• Larger exchange energy
• Smaller coulombic repulsion energy
• Exchange energy: Two or more electrons with the same spin tend to exchange their positions,
and the energy released due to this exchange is known as exchange energy.
The number of exchanges that can take place is maximum when the subshell is either half-filled
or completely filled.
• Diamagnetic species: If two electrons are paired together in an orbital, or their total spin is
zero, then they are diamagnetic electrons. Species with all diamagnetic electrons are known
as diamagnetic species.
• Paramagnetic species: If any of the electrons are unpaired in a species, then these species are
known as paramagnetic species.
• Some exceptional electronic configurations
24
Cr = [Ar] 3d5 4s1
29
Cu = [Ar] 3d10 4s1
To achieve half-filled and fully-filled configuration in orbitals as 3d5 and 3d10, chromium and
copper have exceptional electronic configuration.

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