C H E M I S T R Y

ATOMIC STRUCTURE
WRITING CONFIGURATIONS

What you already know What you will learn

• Limitation of Bohr’s model • Rules of filling the electrons

• Quantum mechanical model • Aufbau principle
• Quantum numbers • Pauli’s exclusion principle
• Orbits and Orbitals • Hund’s rule of maximum multiplicity
• Electronic configuration

NEET BOARDS
Rules of Filling the Electrons

As we know, there are many types of elements known and all the elements have one common
property that they consist of three types of particles that are given as:

Type of Particles

Electron Proton Neutron

The fundamental criteria to differentiate these elements is the number of protons present in the
nucleus. There is also one concept for a neutral atom that the number of protons is equal to the
number of electrons. Neutrons and protons together are known as nucleons which are found in
the nucleus, but the electrons that take part in chemical reactions are present outside the nucleus
in different orbitals.

Rules of filling the

electrons

Pauli’s exclusion Hund’s rule of

Aufbau principle
principle maximum multiplicity

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NEET BOARDS
Aufbau Principle

• Aufbau is a German word that means building up. According to the Aufbau principle, the
available atomic orbitals with the lowest energy levels are occupied before those with higher
energy levels.
• It states that electrons are filled into atomic orbitals in the increasing order of orbital energy
level.
• Electrons first occupy the lowest energy orbital available to them and enter into higher energy
orbitals only after the lower energy orbitals are fully filled.

NEET BOARDS
Energies of Subshells of H-like Species

Those atoms that have only one electron as in H, He +, Li 2+, etc are known as single electron species
and the energy of orbitals in these species depend only upon the principal quantum number (n). It
means that the energy of all the subshells that are present in the same shell is the same.
Energy ∝ Principal quantum number

1s < 2s = 2p < 3s = 3p = 3d
Order of energy
< 4s = 4p = 4d = 4f < ...

Order of energy for H-like species

NEET BOARDS
Degenerate Orbitals

The orbitals that have the same energy are known as degenerate orbitals. So, in H-like species,
i.e., species having only one electron, orbitals having the same principal quantum number are
degenerate orbitals.
For example: (2s and 2p), (3s, 3p and 3d) are degenerate orbitals.
Explanation:
In the above example, we can say that 2s and 2p have the same principal quantum number. Due
to this, both the orbitals have the same energy. Hence, they are known as degenerate orbitals.
Similarly, 3s, 3p and 3d have the same principal quantum number, so these are also known as
degenerate orbitals.

Note

Degeneracy is known as the number of the orbital that have the same energy. It is a numerical
value.

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 03

4s 4p 4d 4f

3s 3p 3d
Energy
2s 2p

1s

Fig. 1: Energies of subshells of H-like species

NEET BOARDS
Energies of Subshells of Multi-electron Species

Those species that have more than one electron are known as multi-electron species. In this
case, the energy of electrons depends on both, principal quantum number (n) as well as azimuthal
quantum number (l) because 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. This can be explained by (n + l) rule or
Bohr-Bury rule which states 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.
• For different (n + l) values
Those subshells that have a lower value of (n + l) have lower energy or we can say that
electrons are filled in those subshells that have the least value of (n + l).
Energy ∝ (n + l)

3d n+l = 3+2 = 5

4s n+l = 4+0 = 4

Value of (n + l) for:
4s will be filled before 3d
3d > 4s
because it is of lower energy
Example of (n + l) rule

• For same value of (n + l)

For those subshells that have the same value of (n + l), the energy depends upon only the
principal quantum number (n). Lower the value of the principal quantum number, lower is
the energy of subshell. Hence, the subshells that have a less value of the principal quantum
number will be filled first than those that have a higher value of the principal quantum number.
Energy ∝ Principal quantum number (n)

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3d n+l = 3+2 = 5

4p n+l = 4+1 = 5

Value of (n + l) for:
3d will be filled first
3d = 4p
due to lower ‘n’ value
Example of orbitals having same (n + l) value

Example: Finding the energy order of different subshells:

1s < 2s

2p < 3d

4f > 4d

5d > 4f

3d < 4p

Comparison of orbital energy

Explanation:
(a) 1s has lower energy than 2s because if we calculate the (n + l) value of both the orbitals, then
the l value for both the s-orbitals will be 0. So, the energy directly depends upon the n value.
An orbital that has a higher value of n will have a higher energy.
(b) 2p has lower energy than 3d because the (n + l) value for 2p is 2 + 1 = 3 but for 3d, it is
3 + 2 = 5. So, the 3d-orbitals has a high value of (n + l). Hence, 3d has higher energy than 2p.
(c) 4f has higher energy than 4d because the value of n is the same for both. So, the energy
directly depends upon the l value. We know that f-orbitals (l = 3) has a higher value of l than d
orbital (l = 2). Hence, 4f has higher energy than 4d.
(d) 5d has higher energy than 4f because the (n + l) value for 5d is 5 + 2 = 7 and for 4f is
4 + 3 = 7, which is the same. Now, we know that if the (n + l) value is same for both cases,
then the energy can be defined by the value of n. Orbital that has a high value of n has a high
energy. So, 5d has higher energy than 4f.
(e) 4p has higher energy than 3d because the (n + l) value for 4p is 4 + 1 = 5 and for 3d is
3 + 2 = 5, which is the same. Now, if the (n + l) value is same for both cases, then the energy
can be defined by the value of n. Orbital that has a high value of n will have a high energy. So,
4p has higher energy than 3d.
If we plot the energy level diagram for the multi-electron species, then it gives a trend according
to the (n + l) value which means as the (n + l) value increases, the energy of the orbitals increases.
This can be shown as in Fig. 2.

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1s
4p 2s 2p
3d 3s 3p 3d
4s
3p 4s 4p 4d 4f
Energy 3s 5s 5p 5d 5f

2p 6s 6p 6d
2s
7s 7p

1s 8s

Fig. 2: Energies of subshells of multi-electron species Fig. 3: Energy trend of orbitals

Trick to Remember: This (n + l) rule for multi-electronic species can be elaborated using a trick
which was given by a famous scientist, Erwin Madelung. Using this, we can easily find the energy
order of different subshells in the multi-electron species as shown in Fig. 3.
Hence, the energy of different orbitals can be arranged in the increasing order as follows:
1s < 2s < 2p < 3s < 3p < 4s < 3d < 4p < 5s < 4d < 5p < 6s < 4f < 5d < 6p < 7s < 5f < 6d < 7p < 8s

Finding the correct statement regarding d-orbital

In a 3d-subshell, all the five orbitals are degenerate. What does it mean?
(a) All the orbitals have the same orientation. (b) All the orbitals have the same shape.
(c) All the orbitals have the same energy. (d) All the orbitals are unoccupied.

Solution

(a) Degeneracy does not tell any information about orientation. All the five orbitals of the d-subshell
have different orientation because each orbital has different value of the ml. There are two
types of orientation possible, one is in between the axis and other is along the axis. So, option
(a) is not correct.
(b) Degeneracy does not tell any information about shape. dz2 orbital has different shape than the
other four orbitals of d-subshell. All the four d-orbitals other than dz2 have double dumbbell
shape. So, option (b) is not correct.
(c) Degenerate orbitals are the orbitals having the same energy. So, option (c) is correct.
(d) Degeneracy does not tell us about the filling of the orbital. Orbitals can be fully filled, half-filled,
partially filled, or they can also be unoccupied. So, option (d) is not correct.
Hence, option (c) is the correct answer.

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Finding the degeneracy of hydride ion

Degeneracy of the second excited state of H− is y. Find the value of y.

(a) 3 (b) 9 (c) 5 (d) 4

Solution

Hydrogen contains one electron, and its electronic configuration is 1s1. When one electron is added
to H, it becomes H−, also known as hydride ion, which will contain 1 + 1 = 2 electrons, having
electronic configuration 1s2. 1s is the ground state, 2s will be the first excited state, and 2p will be
the second excited state for the electrons in H− ion. Second excited state of H−, i.e., 2p-subshell
consists of three degenerate orbitals. So, degeneracy of the second excited state of H− is 3.
Hence, option (a) is the correct answer.

Note

Number of degenerate orbitals having the same energy is known as degeneracy.

NEET BOARDS
Pauli’s Exclusion Principle

Pauli’s exclusion principle states that in a single atom, no two electrons will have an identical
set of all the four quantum numbers (n, l, ml and ms) or orbital of an atom can accommodate
maximum two electrons with opposite spins.
The two electrons in an orbital can have the same value of three quantum numbers n, l and ml
but must have the opposite spin quantum number. The restriction imposed by Pauli’s exclusion
principle on the number of electrons in an orbital helps in calculating the capacity of electrons to
be present in any subshell.
There are two salient rules that the Pauli’s exclusion principle follows:
• Only two electrons can occupy the same orbital.
• The two electrons that are present in the same orbital must have opposite spins or it should
be antiparallel.

Note

Pauli’s exclusion principle does not only apply to electrons. It applies to other particles of half-integer
spin broadly classified as fermions.

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Example: The possible quantum numbers in 3pz orbitals having 2 electrons

Quantum number First electron Second electron

n 3 3

l 1 1

m 0 0

1 1
s + −
2 2

Table 1: Illustration of Pauli’s exclusion principle

According to this table, we can say that if two electrons

occupy the same orbital, then they can have a maximum
three types of the same quantum numbers which are
×
n, l, ml but the value of the fourth quantum number, i.e.,
the spin quantum number cannot be the same for two
electrons.
Filling of electrons in an orbital
In the given representation, consider that both the electrons are present in the same orbital. So, the
value of the quantum numbers n, l, ml and s are same. therefore, the first representation is wrong
and the second is correct because according to Pauli’s exclusion principle, two electrons cannot
have the same set of all the four quantum numbers. In the first case, both the electrons have the
same spin quantum number because they have the same spin, so this is not correct according to
Pauli’s principle. However, in the second case, the electrons have opposite spins and due to this,
they have different spin quantum numbers which is correct according to Pauli’s exclusion principle.

NEET BOARDS
Subshell Electron Capacity

This is defined as the maximum number of electrons occupied by the subshell. Generally, we deal
with only four types of subshells which are s, p, d and f. s, p, d and f have 1, 3, 5 and 7 orbitals
respectively. Each orbital can have a maximum of two electrons and it can have a minimum of zero
electrons. Hence, the electron capacity of the subshell is given as follows:

Name of subshell Number of orbitals Maximum number of electrons

s 1 2

p 3 6

d 5 10

f 7 14

Table 2: Number of orbitals and maximum number of electrons for a given subshell

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NEET BOARDS
Maximum Number of Electrons in any Shell

This is simply a calculation of the number of electrons that can be found in any shell. We already
know that subshells are found in shells and by the help of quantum numbers, we can say that
for nth shell, the number of subshells is decided by l values which varies between 0 to (n - 1). Each
orbital can have a maximum of two electrons. So, the formula to find the number of electrons in any
nth shell is given as follows:
Number of electrons in nth shell = 2n2
Where, n = Shell number (Principal quantum number)

Shell Subshell Number of electrons

1 1s 2 × (1)2 = 2

2 2s, 2p 2 × (2)2 = 8

3 3s, 3p, 3d 2 × (3)2 = 18

4 4s, 4p, 4d, 4f 2 × (4)2 = 32

Table 3: All the possible subshells and number of electrons for a given shell

BOARDS
Hund’s Rule of Maximum Multiplicity

According to this rule, if two or more orbitals have the same energy (degenerate orbitals), then the
filling of electrons happens in such a way that electron pairing will not take place in the orbitals in
that subshell until each orbital is occupied by one electron with parallel spins.
This means that in the lowest possible energy state or ground state, the electron will have the
greatest possible value of spin multiplicity.
In other words, when degenerate orbitals are available, they are singly occupied first with parallel
spins before pairing starts.

NEET BOARDS
Spin Multiplicity

Spin multiplicity is calculated by the total spin of an atom and it depends upon the number of
unpaired electron present in that atom.

1
Total spin (S)= ×n
2

Where n = Number of unpaired electrons

The formula of spin multiplicity can be written in terms of spin of atom as follows:

Spin multiplicity (S.M.) = 2 × |S| + 1

Where S = Total spin of an atom

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We can also write it in the form of unpaired electrons by putting the value of the spin in spin
multiplicity formula, as follows:

1 
Spin multiplicity= 2  × n  + 1
2 
= n+1

As the spin multiplicity increases, the stability of the atom is more.

This can be explained using the following example:

N ⥮ ⥮ ↿ ↿ ↿
For nitrogen (7N), the electronic
configuration = 1s2 2s2 2p3 1s 2s 2p
Orbital diagram for nitrogen

From the diagram, we can see that there are three unpaired electrons in the 2p-orbitals of nitrogen
atom. So, the total spin and spin multiplicity of nitrogen is:

1
Spin of an atom having n unpaired electrons= ×n
2
For three unpaired electrons:
1
Total spin= ×3
2
3
=
2
= 2S + 1
Spin multiplicity
 3
= 2 ×  + 1
 2
S.M. = 4
S.M

Now, consider another case, where the electronic configuration of N is 1s2 2s2 2px2 2py1. This electron
configuration does not follow the Hund’s rule (i.e., in case of degenerate orbitals, electrons are
singly filled first and then only pairing starts). Here, the number of unpaired electrons is 1. So, the
spin (S) is ½. Thus, the spin multiplicity becomes 2. The spin multiplicity is lower than the above
case, where 3 unpaired electrons were there. Therefore, this is not considered to be the ground
state for Nitrogen.

BOARDS
Electronic Configuration

The electronic configuration of an element describes the filling up of subshells of atoms with
electrons. Electronic configurations of atoms follow a standard notation in which all the electron-
containing atomic subshells (with the number of electrons they hold written in the superscript) are
placed in a sequence.

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Example: The electronic configuration of sodium (Na) is 1s2 2s2 2p6 3s1.
There are two ways to write the electronic configuration of any atom which are as follows:
1. sa pb dc… notation (nlx notation, where n is principal quantum number, l is azimuthal quantum
number, and x is number of electrons in subshell)
2. Orbital diagram notation

Two ways of representing

electronic configuration

sa pb dc… notation Orbital diagram

notation

Methods to write electronic configuration

BOARDS
sa pb dc… Notation

In this notation, a similar subshell represented for different shells is differentiated by simply writing
the principal quantum number before the respective subshell.
Example:

19

9
F 1s2 2s2 2p5 5
Fluorine
2 p

Subshell belongs to p-subshell (l = 1) Number of

2nd shell (n = 2) electron = 5
Fig. 4: sa pb dc… notation
Explanation:
Fluorine has nine electrons. According to Aufbau principle, the energy order of the orbitals is
1s < 2s < 2p. The first two electrons will go into 1s and the next two will go into 2s because an
s-subshell can occupy only two electrons and now it has only five electrons left which will go into
2p-orbitals.
This notation is written as nSe.
Where, n = Principal quantum number
S = Name of subshell
e = Number of electrons

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NEET BOARDS
Orbital Diagram Notation

In this method, we draw a box for each orbital and the number of boxes depend upon the orbitals
present in the subshell. Then we fill the electrons according to Aufbau, Hund’s and Pauli’s principle.
The electrons in each orbital are denoted by a half arrow. There are two types of spin possible for
the electrons: namely up spin and down spin. Arrows notation are used to denote these two spins.
Example:

F ⥮ ⥮ ⥮ ⥮ ↿
1s2 2s2 2p5
Orbital diagram notation

Electronic configuration of various elements

1. Hydrogen (H) (Atomic number 1) = 1s1

The hydrogen atom has only one electron that goes in H ↿
the orbital with the lowest energy which is 1s according
to the Aufbau principle. Then, electronic configuration 1s1
of the hydrogen atom is 1s1, meaning that it has one Electronic configuration of H
electron in the 1s-orbital.
2. Helium (He) (Atomic number 2) = 1s2
The helium atom has two electrons that go in the
orbital with the lowest energy which is 1s according to He ⥮
the Aufbau principle and s-orbital can only have two
1s2
electrons. Then, electronic configuration of the helium
atom is 1s2, meaning that it has two electrons in the Electronic configuration of He
1s-orbital.
3. Lithium (Li) (Atomic number 3) = 1s2 2s1
First two electrons are filled in 1s-orbital as in the He Li ⥮ ↿
atom. The third electron of lithium (Li) is not allowed
in the 1s-orbital because of Pauli’s exclusion principle. 1s2 2s1
It therefore takes the next available choice, namely Electronic configuration of Li
the 2s-orbital. Then electronic configuration of lithium
atom is 1s2 2s1.
4. Nitrogen (N) (Atomic number 7) = 1s2 2s2 2p3
Nitrogen has seven electrons. Now, according to
the Aufbau principle, the energy order of orbitals is
1s < 2s < 2p. So, according to this, the first two electrons N ⥮ ⥮ ↿ ↿ ↿
go into 1s-orbital because s-orbital can have only two
1s2 2s2 2p3
electrons, and then the next two will go into 2s-orbital.
After this, only three electrons are left which will be Electronic configuration of N
filled in the 2p-orbital according to Hund’s rule of
maximum multiplicity.

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Similarly, we can write the electronic configuration of other elements as follows:

Atomic Name of Electronic

Symbol Orbital diagram
number element configuration

4 Be Beryllium 1s2 2s2

Be ⥮ ⥮
1s2 2s2

5 B Boron 1s2 2s2 2p1

B ⥮ ⥮ ↿
1s2 2s2 2p1

6 C Carbon 1s2 2s2 2p2

C ⥮ ⥮ ↿ ↿
1s2 2s2 2p2

7 N Nitrogen 1s2 2s2 2p3

N ⥮ ⥮ ↿ ↿ ↿
1s2 2s2 2p3

8 O Oxygen 1s2 2s2 2p4

O ⥮ ⥮ ⥮ ↿ ↿
1s2 2s2 2p4

9 F Fluorine 1s2 2s2 2p5

F ⥮ ⥮ ⥮ ⥮ ↿
1s2 2s2 2p5

10 Ne Neon 1s2 2s2 2p6

Ne ⥮ ⥮ ⥮ ⥮ ⥮
1s2 2s2 2p6

11 Na Sodium 1s2 2s2 2p6 3s1

Na ⥮ ⥮ ⥮ ⥮ ⥮ ↿
1s2 2s2 2p6 3s1

12 Mg Magnesium 1s2 2s2 2p6 3s2

Mg ⥮ ⥮ ⥮ ⥮ ⥮ ⥮
1s2 2s2 2p6 3s2
Table 4: Electronic configuration and orbital diagrams of some elements

NEET BOARDS
Simplified Electronic Configuration

While writing the simplified electronic configuration of any atom, we can replace the electronic
configuration up to the nearest noble gas (having less electrons than atom) with the noble gas
symbol and we only write the electronic configuration of the valence shell.
Noble gas is defined as the element which has a complete octet (ns2 np6) outer configuration. For
example, He (which only has a doublet as it has only two electrons), Ne, Ar, Kr, Xe and Rn. The
electronic configuration of different noble gases can be written as follows:
2
He = 1s2
10
Ne = 1s2 2s2 2p6
18
Ar = 1s2 2s2 2p6 3s2 3p6

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Example of simplified electronic configuration:

1. 11Na: Sodium has 11 electrons. Now, according to the Aufbau principle, the energy order of orbitals is
followed as 1s < 2s < 2p < 3s. So, according to this, the first two electrons will be filled in 1s-orbital as
s-subshell has only one orbital that can accommodate only two electrons. The next two electrons
will be filled in 2s-orbital and the next six will be filled in 2p-orbital because a p-subshell can
accommodate a maximum of six electrons. After this, we are left with one electron which goes into
3s-orbital as per the Aufbau principle.

Na ⥮ ⥮ ⥮ ⥮ ⥮ ↿
1s2 2s2 2p6 3s1

Ne
Electronic configuration of Na
So, the electronic configuration of Na is [Ne] 3s1.
2. 18Ar: Argon has 18 electrons. Now, according to the Aufbau principle, the energy order of
orbitals is followed as 1s < 2s < 2p < 3s < 3p. So, according to this, the first two electrons will
be filled into 1s-orbital because s-subshell has only one orbital that can accommodate only
two electrons. The next two electrons will be filled into 2s-orbital and the next six will go
into 2p-orbitals because a p-subshell can accommodate a maximum of six electrons. Then
two electrons will be filled in 3s-orbital. After this, we are left with six electrons which go into
3p-orbitals because the p-subshell can accommodate a maximum of six electrons.

Ar ⥮ ⥮ ⥮ ⥮ ⥮ ⥮ ⥮ ⥮ ⥮
1s2 2s2 2p6 3s2 3p6

Ne

Electronic configuration of Ar
So, the electron configuration of Ar is [Ne] 3s2 3p6.

Finding electronic configuration, unpaired electrons, and total spin

Write the electronic configuration and find the number of unpaired electrons as well as the total
spin for the following atoms:
(a) 21Sc (b) 26Fe

Solution

(a) Step 1: Finding the electronic configuration of Sc

Arrange the subshells in the ascending order of their energies following the (n + l) rule. If there is a
tie for the value of (n + l), then the subshell with the smaller value of n has the lower energy.
1s < 2s < 2p < 3s < 3p < 4s < 3d < 4p < 5s < 4d < 5p < 6s

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Lower energy subshells are filled prior to the higher energy subshells and electron pairing
starts in orbitals in a subshell after every orbital of the subshell gets half-filled. Hence, electronic
configuration of Sc can be given as follows:
21
Sc = 1s2 2s2 2p6 3s2 3p6 4s2 3d1
= [Ar] 4s2 3d1 (Where electronic configuration of Ar = 1s2 2s2 2p6 3s2 3p6)
= [Ar] 4s2 3d1
Hence, the simplified configuration for 21Sc = [Ar] 4s2 3d1

Step 2: Finding the the number of unpaired electrons

The valence shell orbital diagram for 21Sc can be shown as follows:

[Ar] ⥮ ↿
4s2 3d1
Orbital diagram for Sc

From the orbital diagram, we can see that the number of unpaired electrons = 1

Step 3: Finding the total spin of atom

Since the total number of unpaired electrons in Sc is 1,
1 1
Total spin = + or −
2 2

(b) Step 1: Finding the electronic configuration of Fe

Electronic configuration of Fe can be given as follows:
26
Fe = 1s2 2s2 2p6 3s2 3p6 4s2 3d6
= [Ar] 4s2 3d6 (Where electronic configuration of Ar = 1s2 2s2 2p6 3s2 3p6)
= [Ar] 4s2 3d6
Hence, the simplified configuration for 26Fe = [Ar] 4s2 3d6

Step 2: Finding the the number of unpaired electrons

The valence shell orbital diagram for Fe can be shown as follows:

[Ar] ⥮ ⥮ ↿ ↿ ↿ ↿
4s2 3d6
Orbital diagram for Fe

From the orbital diagram, we can see that the number of unpaired electrons = 4

Step 3: Finding the total spin of atom

 1 1 4 4
Total spin =  − or +  × 4 =+ or − = +2 or -2
 2 2 2 2

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NEET BOARDS
Anomalous Electronic Configuration

There are some exceptions in the electronic configuration. These exceptions depend upon a
simple concept that says that if any atom has half-filled or fully filled orbitals in a subshell, then it
has extra stability due to symmetry and exchange energy. Hence, we can say,
• d5 is more stable than d4.
• d10 is more stable than d9.
Examples:
• Chromium, Z = 24 (24Cr)
According to the mentioned principles (Aufbau, Hund’s, and Pauli’s), the simplified electronic
configuration for 24Cr can be written as [Ar] 4s2 3d4 but this is not correct. The correct electronic
configuration of 24Cr can be written as [Ar] 4s1 3d5 in which from our expected electronic
configuration a 4s electron has been promoted to 3d-subshell. This is because, after the transfer
of this electron from 4s to 3d, the electronic configuration for both the orbitals become half-filled
and we know that half-filled and fully filled orbitals in a subshell are more stable than partially
filled orbitals. Hence, this configuration is more stable than the expected configuration predicted
by general principles/rules.

Cr [Ar] 4s2 3d4

24 Expected
52
Cr
24

24
Cr [Ar] 4s1 3d5 Observed

Exception in electronic configuration of Cr

• Copper, Z = 29 (29Cu)
According to the general principles (Aufbau, Hund’s, and Pauli’s), the simplified electronic
configuration for 29Cu can be written as [Ar] 4s2 3d9 but this is not the observed configuration.
The correct electronic configuration of 29Cu can be written as [Ar] 4s1 3d10 in which a 4s electron
has been promoted to 3d-subshell. This is because, after the transfer of this electron from 4s
to 3d, the electronic configuration for the subshells become half-filled and fully filled. Now, half-
filled and fully filled orbitals in subshells are more stable than partially filled orbitals. Hence, this
configuration is more stable than the configuration we expected based on rules.

29
Cu [Ar] 4s2 3d9 Expected
63

29
Cu
29
Cu [Ar] 4s1 3d10 Observed

Exception in electronic configuration of Cu

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BOARDS
Extra Stability of Half-filled and Fully filled Orbitals

As discussed earlier, exactly half-filled and fully filled orbitals have higher stability than the others.
Hence, p3, p6, d5, d10, f 7 and f 14 are more stable than other partially filled orbitals configuration.
There are two reasons behind this, which are as follows:
1. Symmetry
2. Exchange energy

BOARDS
Symmetry

According to this, the half-filled and fully filled orbitals have symmetry in the distribution of the
electron density and the symmetrical distribution of electrons increases the stability of the atom.
This is because, due to the symmetrical distribution, there will be less shielding effect and effective
nuclear charge observed by the outermost electron will increase. Hence, the electrons are very
strongly bound and this leads to high stability.

Note

In a multi-electron atom, the electrons of the valence shell are attracted to the nucleus and these
electrons are also repelled by the electrons present in the inner shells. On account of this, the
actual force of attraction between the nucleus and the valence electrons is somewhat decreased
by the repulsive forces acting in opposite directions. This decrease in the force of attraction
exerted by the nucleus on the valence electrons due to the presence of electrons in the inner
shells is known as screening effect or shielding effect.
The magnitude of the screening effect depends upon the number of inner orbital electrons and
how diffused the electron density is in these inner orbitals. Higher the number of inner electrons
and less diffused is the electron density, greater will be the value of the screening effect and lower
will be effective nuclear charge.

BOARDS
Exchange Energy

The exchange interaction is a quantum mechanical effect that only occurs between identical
particles. Exchange energy is the energy released when two or more electrons with the same
spin exchange their positions in the degenerate orbitals of a subshell. So, due to the release in
the energy, they gain extra stability. More the number of exchanges taking place, more will be the
energy released and more stable will be the given electronic configuration.
The number of exchanges that can take place is maximum when the subshell is either half-filled or
completely filled which can be shown in Fig. 5. In this, if we give the name of all five electrons as a,
b, c, d and e, then we can clearly see that a, b, c, d and e electrons have 4, 3, 2, 1 and 0 exchanges.
So, the total number of exchanges for d5 is 10. If another configuration is present, then the number
of exchanges taking place will be less than 10. Hence, the exchange energy will be less and the
electronic configuration will be less stable.

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 17

a b
↿ ↿ ↿ ↿ ↿ ↿ ↿ ↿ ↿ ↿
4 exchanges by electron ‘a’ 3 exchanges by electron ‘b’

c d
↿ ↿ ↿ ↿ ↿ ↿ ↿ ↿ ↿ ↿
2 exchanges by electron ‘c’ 1 exchange by electron ‘d’
Fig. 5: Exchange possibilities in d5 system

Application of Hund’s rule and Aufbau principle

Which is the orbital diagram in which both Hund’s rule and Aufbau principle are violated?

⥮ ⥮ ↿ ↿ ⥮ ↿ ↿
(a) (b)
2s 2p 2s 2p

↿↿ ↿ ↿ ↿ ↿ ⥮ ⥮
(c) (d)
2s 2p 2s 2p

Solution

Violating Hund’s rule means pairing of electrons started in spite of degenerate orbitals being
available and are not occupied.
Violating the Aufbau principle means electrons are not filled according to the increasing order of
the energy.
a) Pairing of electrons started when all 2p-orbitals are not singly occupied. That is the violation
of Hund’s law but Aufbau principle is followed because filling of electrons has been done from
lower energy to higher energy level. Both Hund’s rule and Aufbau principle are not violated.
Hence, option (a) is not correct.
b) In this option, in the p-subshell, pairing of electrons takes place after it is half-filled. That is not a
violation of Hund’s rule and the electrons are not filled according to the Aufbau principle. Thus,
Aufbau principle is violated but Hund’s rule is not violated. So, option (b) is not correct.
c) In this option, the 2p-orbital is half filled and there is no pairing of electrons, also electrons are
filled in the orbital according to Aufbau principle even though Pauli’s principle is violated. That
is but not a violation of Hund’s rule and the Aufbau principle. So, option (c) is not correct.
d) Pairing of electrons started when there is an empty 2p-orbital. That is the violation of Hund’s rule.
The electrons are not filled according to the increasing order of energy as 2s is not completely
filled, so violation of the Aufbau principle also takes place.
Hence, option (d) is correct.

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Summary

The following are the rules that need to be followed while filling electrons in orbitals:
• Aufbau principle
• Pauli’s exclusion principle
• Hund’s rule of maximum multiplicity
Aufbau principle:
It states that electrons are filled into different atomic orbitals in the increasing order of the orbital
energy level.
Generally, the atoms can be divided into two categories on the basis of the number of electrons
which are given as follows:
• Having only one electron which are known as H-like species and energy of orbitals in these
species is depend only upon the principal quantum number.
• Having more than one electron which are known as multi-electron species and energy of
these species is dependent upon the value of the (n + l) also known as Bohr-Bury rule.

Note

The energy of different subshells can be arranged in the increasing order as:
1s < 2s < 2p < 3s < 3p < 4s < 3d < 4p < 5s < 4d < 5p < 6s < 4f < 5d < 6p < 7s < 5f < 6d < 7p < 8s

Pauli’s exclusion principle:

It states that in a single atom, no two electrons can have an identical set or the same set of quantum
numbers (n, l, ml and ms). To put it in simple terms, every electron should have or be in its own
unique quantum state (singlet state).
• The maximum number of electrons occupied by a subshell is known as the electron capacity
of the subshell. Generally, we deal with only four types of the subshells that are s, p, d and
f which have 1, 3, 5 and 7 orbitals, respectively. Each orbital can have a maximum of two
electrons.
• The formula to find the number of electrons in the nth shell is given as follows:
Number of electrons in nth shell = 2n2
Where n is the principal quantum number
Hund’s rule of maximum multiplicity:
According to this rule, if there are two or more than two orbitals that have the same energy
(degenerate orbitals), then the filling of electrons happens in such a way that electron pairing will
not take place in the orbitals in a subshell until each orbital in it is occupied by one electron each
with parallel spin.
Electronic configuration:
The electronic configuration of an element describes how electrons are distributed in their atomic
orbitals. Electronic configuration of atoms follow a standard notation in which all the electron-
containing atomic subshells (with the number of electrons they hold written in the superscript) are
placed in a sequence.
For example, the electronic configuration of sodium (Na) is 1s2 2s2 2p6 3s1.

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There are two ways to write the electronic configuration of any atom, which are given as follows:
• sa pb dc…. notation (nlx notation)
• Orbital diagram notation
Anomalous electronic configuration:
There are some exceptions in the electronic configuration. These exceptions are based upon a
simple concept that says that if any atom has half-filled or fully filled orbitals in a subshell, then it
has extra stability due to symmetry and exchange energy. Hence, we can say that,
• d5 is more stable than d4.
• d10 is more stable than d9.
Example: 24Cr, 29Cu
Extra stability of half-filled and fully filled orbitals:
As discussed earlier, exactly half-filled and fully filled orbitals in a subshell would have higher
stability than the others. Hence, p3, p6, d5, d10, f 7 and f 14 are more stable than other partially filled
orbitals configuration.
There are two reasons behind this, which are as follows:
1. Symmetry
2. Exchange energy

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