CHEMISTRY

Atomic
Structure
Ch 4 Session 4 01 June 2020
ATOMIC ORBITALS & QUANTUM
NUMBERS
 Orbital ⟶ Three dimensional space around the nucleus in which the
probability of finding the electron is maximum

 An atomic orbital can be completely described in terms of a set of 3

Quantum numbers whereas
for an electron a 4th quantum number needs to be specified.

Quantum numbers
assigned
Orbital n, l & ml
Electron n, l, ml & ms 3
ATOMIC ORBITALS & QUANTUM
NUMBERS
1. Principal Quantum number(n):
 Identifies shell / level / orbit.

 Can have values n = 1, 2, 3, 4.........

 Can have symbols n = K, L, M, N......

 The no. of orbitals allowed = n2

 The no. of electrons in each shell = 2n 2

n Symbol no. of orbitals = Size of the shell

n2
1 K 1 increases as value
2 L 4 of n increases

3 M 9
4
4 N 16
ATOMIC ORBITALS & QUANTUM
NUMBERS
2. Azimuthal Quantum number / Subsidiary number (l):
 Identifies sub - shell / sub - level

 Can have values l = 0 to (n-1)

 No. Of subshells = n

eg: If n = 3, then three subshells are possible with different values of

l
Symbo n l = 0 to (n-1)
l 0, 1, 2 & 3 is s, p, d &
K n=1 l = 0 (s) f
L n=2 l = 0 (s)
⸫ 2 subshells
l = 1 (p)
M n=3 l = 0 (s)
⸫ 3 subshells
l = 1 (p) 5

l = 2 (d)
ATOMIC ORBITALS & QUANTUM
NUMBERS
3. Magnetic Quantum number (ml):
 Identifies orbital
 Relative spatial orientation of orbitals in a given subshell.

 m = -l to +l

 no. of orbitals in subshell is given by (2l + 1)

 no. of electros in each orbital = 2

Symbol n l = 0 to (n-1) ml
K n=1 l = 0 (s) ml can have (2l + 1)values. ⸫ 1 orbital ⸫ ml
=0
L n=2 l = 0 (s) (2l + 1) values. ⸫1 orbital ⸫ ml =
0
l = 1 (p) (2l + 1) values. ⸫3 orbitals ⸫ ml =-1,
6
0, +1
M n=2 l = 0 (s) ⸫ ml = 0
Atomic Orbitals & Quantum Numbers
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Principal Quantum Azimuthal Quantum Magnetic Quantum no.

no. no. /
Subsidiary Quantum
no.
n l ml
Identifies shell / level/ Identifies subshell / sublevel Identifies orbital
orbit
Values n = 1, 2, 3, 4...... Values l = 0 to (n – 1) Values ms = – l to +l
Symbols n = K, L, M & N l = s, p, d & f

The no. of orbitals allowed No. of subshells = n No. Of orbitals in a subshell

= n2 eg: If n = 3, =
3 subshells are possible with (2l + 1)
different values of l
ATOMIC ORBITALS & QUANTUM
NUMBERS
4. Electron spin Quantum number (ms):
 Specifies spin state of the electron in an orbital

 An electron can spin around its axis

 Two spin states can be either + ½ or – ½

 These can be represented by arrows.: ↑ (+ ½ ) & ↓ (– ½ )

 “An orbital can accommodate maximum two electrons and they must have
opposite spins” – Pauli’s exclusion principle.
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Atomic Orbitals & Quantum Numbers
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Summary of the all the formulas

No. of subshells in a shell = n

No. of orbitals allowed in a shell = n2

No. of orbitals allowed in a subshell = (2l + 1)

No. of electrons in a shell = 2n2

No. of electrons in an orbital = 2
ATOMIC ORBITALS & QUANTUM
NUMBERS
Orbital distribution diagram - explained during the lecture

Numerical: (discussed & solved during the lecture)

 Problem 4.9: How many orbitals make the N shell? What is the

subshell wise distribution of orbitals in the N shell?

 Problem 4.10: An atom has two electrons in its 4s orbital. Write the values of the
four quantum numbers.

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SHAPES OF ATOMIC ORBITALS
1. s - orbitals:
 Spherical in shape

 Size and energy increases with increase in Principal Quantum number

(n)

 In between 1s and 2s there is a region where the probability of finding

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the electron is zero. It is called a node.

SHAPES OF ATOMIC ORBITALS
2. p - orbitals:
 Dumbell shaped

 Three orbitals – p , p & p

x y z
 Their orientations in space are different, 3 orbitals lie along the 3 axes.
 Size and energy of all three orbitals are same.

 Size and energy increases with increase in Principal Q no. (n)

 Each p – orbital has 2 lobes on 2 sides of a nodal plane.

 Nodal plane: A plane having zero electron density.

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SHAPES OF ATOMIC ORBITALS

3. d - orbitals:
 Double dumbell shaped / clover shaped

 Five orbitals – dxy, dyz, dxz, dx2-y2, dz2

 All are equivalent in energy.(degenrate)

 Size and energy increases with increase in Principal Q no. (n) (or they
are said to be more diffused) 13
SHAPES OF ATOMIC ORBITALS
4. f - orbitals:
 Complex

 Seven f – orbitals

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Shapes of Atomic Orbitals

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ENERGIES OF ORBITALS
 Energy of an electron in the Hydrogen atom / Hydrogen like species →
 depends on ‘n’ alone.
 Reason: The only interaction here is between nucleus and electron
For H & H like species: 1s < 2s = 2p < 3s = 3p = 3d < 4s = 4p = 4d =
4f...............

 Energy of an electron in a multi-electron atom → depends on ‘n’ & ‘l’

 Reason: along with interaction between nucleus & electron, there is also

mutual repulsion among the electrons.

 For multi – electron species: ( n + l ) rule is obeyed.

1) Lower the sum of (n + l) for an orbital, lower is its energy

2) If 2 orbitals have same (n+l) values then orbital with lower value of n is of lower
energy.
 Increasing order of energy for orbitals in multi – electron species is as 16

follows:
ENERGIES OF ORBITALS
 In a multi – electron atom, electrons occupy different orbitals.

 The lowest total electronic energy corresponds to the most stable, that is
the ground state of an atom.

 The orbital wise distribution of electrons in the ground state can be

understood by the Aufbau principle.

 Aufbau Principle: comes from the Afbauprinzip – building up / filling up

 The principle is based on (i) – increasing order of energies of orbitals

(ii) – Pauli’s exclusion principle
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(iii) – Hund’s rule of maximum multiplicity
AUFBAU PRINCIPLE – INCREASING ORDER
OF E
 follows (n + l) rule
 Electrons are filled in an increasing order of orbital energy

 Let us learn 2 easy ways to remember this order.

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AUFBAU PRINCIPLE – HUND’S RULE
 Filling of electrons in the orbitals belonging to the same subshell follows
Hund’s rule of maximum multiplicity.

 “Pairing of electrons in the orbitals belonging to the same

subshell does not occur unless each orbital belonging to that
subshell has got one electron each ”

 eg: If we have 4 electrons filling up the p – subshell then, it can be filled in

2 ways↑↓ ↑↓

↑↓ ↑ ↑

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 Note: Half – filled & filled set of degenerate orbitals have extra stability.
ELECTRONIC CONFIGURATION OF ATOMS &
REPRESENTATION
 Electronic configurations: Distribution of electrons in the orbitals of an
atom.

There are two methods of representing electronic configuration:

 Orbital notation method: Principal Quantum number

Symbol of subshell
no. of electrons in the subshell as superscript

 Orbital Diagram method: Each orbital in a subshell is represented by a

box
The electron is represented by an arrow
(↑ for up spin & ↓ for down spin) 21
ELECTRONIC CONFIGURATION OF ATOMS &
REPRESENTATION

 Condensed Electronic configuration: Configuration of a preceding inert

gas in [ ] followed by outer configuration immediately after the bracket.

 Iso – electronic species: Atoms and ions having the same number of
electrons are iso – electronic
 eg: Ar, K+ & Ca2+ are isoelectronic

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ELECTRONIC CONFIGURATION OF ATOMS &
REPRESENTATION
 Problem 4.11: Write electronic configuration of 18 Ar and 19 K using orbital
notation and orbital diagram method.

 Exercise Q (S) pg 54: Indicate the number of unpaired electrons in

a. Si (Z = 14) b. Cr (Z = 24)

 Problem 4.11: Find out one dinegative anion and one unipositive cation
which are isoelectronic with Ne atom. Write their electronic configuration
using orbital notations and orbital diagram method.

 Exercise Q (K) pg 54: Write electronic configurations of Fe, Fe2+, Fe3+.

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