Lecture

Content to be covered
 Definition of quantum numbers
 Orbital and spin angular momentum
 Space quantization
 Spin-orbit coupling
 Designation of states
 Atoms in magnetic field
 Normal Zeeman effect

Resources to be consulted
Concepts of Modern Physics by Arthur Beiser

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 Atomic Structure
• Light emitted from hot body on passing through a prism gives
continuous spectrum.
• After passing through a cool gas some wavelength were
missing in the spectrum of same light.
• Light emitted from a hot gas, bright lines of certain
wavelength were observed through prism.
• Excited atoms emit light of only certain wavelengths.
• The wavelengths of emitted light depend on the element.

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 Hydrogen Atom Spectra
 Absorption spectra have black lines (gaps) on a
bright background, whereas emission spectra
have bright lines on a black background.
 In both types of spectra the lines are in the same
places and also the lines are more closely spaced
toward the blue/violet end of the spectrum.

When an atomic gas or

vapour is excited, the
emitted radiation has a
spectrum which contains
certain specific wavelength
only.

Classical physics can’t

explain this

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 Line Spectra of Excited Atoms

• Bohr model explained well hydrogen atom emission

• In some elements emission spectra has two or three close wavelength
• Two or higher electron elements emission could not be explained by Bohr
model.

Hg

Ne

Find the longest as well as shortest wavelength photon emitted in the Balmer series
and determine corresponding energy.

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 Quantum Numbers

A brief overview of the relationship between the quantum

numbers that come out of the quantum mechanical calculations
and the atomic orbital that used to describe the energies and
probabilities of finding the electrons in an atom.

There are four quantum numbers associated with an electron

n, ℓ, mℓ, ms

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 Principle Quantum Number (n): (By Bohr)

It determines the energy and the average distance between

electron and nucleus, i.e size of the atom.
The maximum number of electrons in an orbit represented by this
quantum number is 2n2.
n  shell K,L,M….Allowed states : Any number

Azimuthal Quantum Number (ℓ)

( ) (by Sommerfield
Sommerfield))
Azimuthal or orbital or angular quantum number.
It determines the number of sub shells or sublevels to which the
electron belongs. It tells about the shape of sub-shells.
ℓ  sub-shell s, p, d, f.. Allowed states: ℓ = 0 to (n-1)
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 Space Quantization
•The orbital or angular momentum quantum number ℓ tells us the
magnitude of the orbital angular momentum ‘L’. Such that
L2= ℓ(ℓ+1)ħ2
•To describe it fully, the direction of this momentum is required.
•We know that when the electron revolves around the nucleus gives
rise to current loop and a magnetic field is associated with it.

•Hence, atomic electron possessing an angular momentum interacts

with this magnetic field.
•The magnetic quantum number mℓ specifies the direction of ‘L’ by
determining the component of ‘L’ in the field direction. This
phenomenon is called SPACE QUANTIZATION.

•Direction of L is perpendicular to the plane of circle.

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 Space Quantization
• Let the direction of magnetic field be parallel to z-axis, then
Lz = mℓ ħ mℓ = -ℓ, (-ℓ+1), …,0, …, (ℓ-1), ℓ
• mℓ :The magnetic quantum number.
• possible values of mℓ = 2ℓ+1 from +ℓ through 0 to –ℓ.

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 Space Quantization
•If ℓ= 0, Lz can have only single value
of 0. If ℓ= 1, Lz has three values ħ, 0
and -ħ.
•It was proposed by Zeeman.
•It gives the number of permitted
orientation of sub-shells.
•The space quantization of a molecule
having ℓ= 2 :

Vector model of orbital

angular momentum

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 Spin Quantum Number : s
• Each electron has an intrinsic angular momentum which is same
for all electron.
• The spin quantum number is defined as s =1/2
• Spin angular momentum S2=s(s+1)ħ2
• The spin motion of the electron around its own axis also
produces a magnetic field
Sz=msħ
ms  The spin projection quantum number
or magnetic quantum number for
spin motion
ms = ±1/2

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 Total Angular Momentum : J
When the orbital angular momentum (ℓ) and spin angular
momentum (s) are coupled, the total angular momentum is of the
general form for quantized angular momentum

J2=j(j+1)ħ2

where, j = total angular momentum quantum number.

such that
j=(ℓ±s) = (ℓ±1/2)
This gives a z-component of angular momentum

Jz=mjħ, mj=-j, (-j+1), …,(j-1), j

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 Total Angular Momentum : J
• As long as external interactions are not extremely strong, the
total angular momentum of an electron can be considered to
be conserved and j is said to be a "good quantum number".

• This quantum number is used to characterize the splitting of

atomic energy levels, such as the spin-orbit splitting which
leads to the sodium doublet.
• Since Jz , Sz and Lz are scalar quantities so
Jz = Lz ± Sz
mj = mℓ ± ms
• since mℓ is an integer and ms is ½; so mj must be half-
integral.

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 L-S Coupling
Two ways to combine L and S are

This phenomenon is called L-S coupling.

"Vector cones" of total angular momentum J
(purple), orbital L (blue), and spin S (green). The
cones arise due to quantum uncertainty
between measuring angular momentum
j ls
components
ls  ls
Pauli exclusion principle
No two electrons can have all their 1 1 3
l  1, s   j  ,
quantum numbers alike. Physics-1
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 Coupling of orbital momenta
Consider two electrons with l1 & l2
L  l1  l2  l1  l2  (l1  l2 )
e.g . if l1  1 & l2  2; then, L  0( S ),1( P ),2( D)

Spin Multiplicity
Indicates the number of possible quantum states of a system with
given principal spin quantum number S.
The different states along any direction are distinguished by the
spin quantum number S, which can take the values -S, (-S+1), ...,(S-
1), S.
ms = 2S+1, where S is the number of singly occupied electrons
multiplied by the Electron Spin Quantum Number, ms.

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 Spin Multiplicity
For S=0  singlet state.
For S=1/2  doublet.
For S=1  triplet, and so on.

The most important application is two electrons.

A single free electron has S=1/2; it is therefore always in a doublet state.

Two electrons can pair up in a singlet or in a triplet state. Normally the
singlet is the ground state.

E.g. oxygen has two singly occupied electrons which could have spin
multiplicity of 3.
This means that the spins could be up-up or up-down or down
down, total 3 possibilities.

Using the formula, Spin Multiplicity of oxygen = 2S+1 = 2(21/2)+1 = 3,

where S= two singly occupied electrons ms (ms always equal to ½).
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Designation of states: For two electron case
Coupling of orbital angular momenta
• ℓ 1  orbital quantum number for first electron
• ℓ 2  orbital quantum number for second electron
After coupling resultant angular momentum:
L = (ℓ 1 - ℓ 2) to (ℓ 1 + ℓ 2)
If ℓ 1 = 1 and ℓ 2 = 1 then L= 0 to 2 Thus L = 0, 1, 2

Coupling of spin angular momenta:

• s1  spin quantum number for first electron
• s2  spin quantum number for second
After coupling resultant angular momentum:
S = (s1 - s2) to (s1 +s2)
If s1 = 1/2 and s2 = 1/2 then S = 0, 1

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