ORBITAL MAGNETIC MOMENT OF AN ATOM

We may roughly consider an atom as an electron charge – e circulating the nucleus with a speedv
. It is equivalent to a circular current loop. The current i in the loop the ratio of the charge to the
periodT .

−e −ev
∴ i= = …(2.1)
T 2 πr
It would give rise to a magnetic dipole moment μl given by

μl ¿ current × area of the loop

−ev
¿ iA= ∙ πr 2 , for a circular orbit
2 πr

evr −e
¿− = mvr
2 2m

e
¿− L …(2.2)
2m
where L=mvr , the magnitude of the orbital angular momentum.
But, the magnetic moment ⃗μl and the angular momentum ⃗
L are both vectors. Therefore,

−e ⃗
μ⃗ l= L …(2.3)
2m
⃗ can have only certain quantized values, μ
Since L ⃗ l also can have certain allowed values only. The
implication of the negative sign is that ⃗μl and ⃗
L are oppositely directed. Using the quantum
L|,
mechanical values for|⃗

|⃗μl| e ⃗
¿− |L|
2m

e
¿−
2m
√ l(l+ 1)ℏ

eℏ
¿−
2m
√ l(l+ 1)
 ¿−μB √ l(l+ 1) …(2.4)
eℏ
where μ B= is called Bohr magneton, the basic unit of atomic magnetic moment and has a
2m
magnitude 9.27 × 10−24 J /T obtained by substituting the values of e, ℏ and m.

From equation (3), the z-component of magnetic moment is given by

e
μlZ ¿− L
2m Z

e
¿− mℏ
2m l

i. e . μlZ ¿−ml μ B …(2.5)

An important result follows from equations (4) and (5). Since√ l(l+ 1)>ml,|⃗μl|> μ Z . It implies that

the magnetic moment |μ

⃗ l| cannot align along the z−¿direction. In a system of atoms, the
magnetic moments of the atoms are oriented at random.

MAGNETIC DIPOLE IN A MAGNETIC FIELD

Let a magnetic dipole of moment μ B. Classically, it will

⃗ l be placed in a magnetic field⃗
experience a potential energyV , the energy of interaction between the magnetic moment and the
magnetic field, given by
V =−⃗μ l ∙ ⃗
B …(2.6)
If B is in the z-direction, then using equation (5), we get
⃗
V =−μ lZ B=m l μ B B …(2.7)
Now, since m l is quantized, the potential energy V is also quantized. Therefore, in a magnetic
field, the atomic state of a given l splits into (2 l+ 1) different states according to the magnetic
quantum numberm l.

LARMOR PRECESSION
If a dipole of magnetic moment ⃗μl is placed in an external magnetic field ⃗
B, it acquires a
potential energy V =−⃗μ l ∙ ⃗
B. Classically, it experiences a torque τ⃗
τ⃗ =⃗μl × ⃗
B …(2.8)
The torque’s role is to align the dipole in the field direction. As ⃗μl and ⃗
L are oriented antiparallel,
τ⃗ would be perpendicular to ⃗μl , ⃗
L and ⃗
B. But we have, from mechanics,
τ⃗ =d ⃗L /dt …(2.9)
Therefore, d L /dt is also perpendicular to ⃗μl , L and Bimplying that d L, the change in angular
⃗ ⃗ ⃗ ⃗
momentum, is in direction of τ⃗ . Since the magnitude of ⃗
L remains the same, its direction must
L. Thus, the change in angular momentum d ⃗L requires the precession of ⃗
undergo change in ⃗ L
about the magnetic field. This is what is known as Larmor precession, the frequency of
precession is logically termed as Larmor frequency, ω L.

Now, ω L ¿ dφ = 1 dL = 1 τ
dt Lsin θ dt L sinθ

1 μl B
¿ ∙ μl B sin θ= …(2.10)
L sin θ L

[using equations (2.1) and (2.2)]

Substituting for L from equation (2), we obtain

ωL ¿
( 2em L) ∙( 1L )∙ B= 2eBm …(2.11)

The cause of precession is this: With the application of the field, ⃗μl tends to align along ⃗
B for
that corresponds to the minimum energy and this tendency of ⃗μl results in rotational energy
which must be dissipated. But there is no available process of energy-dissipation and μ
⃗ l in its
B precesses about⃗
tendency to align along ⃗ B, keeping θ and energy constant.

STERN GERLACH EXPERIMENT

A direct demonstration of the existence of space quantization of angular momentum of the
electron and the electron spin was made by the celebrated experiment conducted by two German
scientists Otto Stern and Walter Gerlach (1922).

Set-up – The experimental set-up is illustrated schematically in Fig. 1. A beam of neutral silver
atoms from an oven O, a neutral atomic beam of silver is directed, after properly collimating it
though a set of slits S1, S2 into an inhomogeneous magnetic field produced between the pole
pieces SN. The S-piece is shaped as a knife edge while the N-piece is provided with a grove.

A photographic plate P is placed behind the field, perpendicular to the knife edge, to record the
configuration of the atomic beam after its passage through the field. The whole arrangement is
enclosed in an evacuated chamber to enable the silver atoms to traverse the field without
collision.

Theory – If a magnetic dipole is placed in a homogeneous magnetic field, the forces on the poles
are equal and opposite. Therefore, no net force acts on the dipole. It experiences a torque and the
result is a rotational motion of the dipole. In a non-homogeneous field, (here along z-axis)
however, the dipole experiences a net resultant force (that varies with its orientation relative to
the field) given by
∂V
FZ ¿−
∂Z …(2.12)
where V is potential energy.

Substituting the value of V from (2.2) in equation (2.12), we obtain

∂V
FZ ¿−
∂Z …(2.13)
dB dB
F Z =μ Z =μ sin θ
dz dz
where μ is the magnetic moment of the atom, μZ the component of μ in z-direction, θ the angle ⃗μ
makes with z-axis and dB / dz the gradient of the magnetic field along the z-axis.

Due to this force F Z , the dipole makes a translational motion in the z-direction. As the net force
on μ depends on the orientations ofμ, the dipoles with different orientations will naturally be
brought to different positions on the photographic plate.
Results and conclusion – The silver atom has only one valence electron. Its ground state l=0
thus gives L=0 andμ=0. Therefore, the dipoles will experience no force along z-direction, and
one would expect that the silver atoms would pass undeflected to give only one line on the
screen. But Stern and Gerlach found in their experiment two distinct lines – one above and the
other below the mean position. It follows that the magnetic moment of silver atom in the ground
state is not zero. The pattern of splitting of the atomic beam on the photographic plate confirms
that the magnetic moment takes up two orientations in the inhomogeneous magnetic field
corresponding to two m S values +1/2 and −1/2. Therefore, over and above the three quantum
numbers n, l, and m l, a forth quantum number ms which can assume the values +1/2 and −1/2
only must be required to describe each atomic state. Stern-Gerlach experiment conclusively
demonstrates the existence of an additional momentum vector which is quantized similar to the
L.
orbital angular momentum ⃗

The splitting gives two short lines on the photographic plate and it is possible to
determine from the distance between the lines, the magnetic moment of silver atoms and hence
the electronic magnetic moment.

Here a question may arise: Could the pattern be produced by spinning particles other than
electrons – Protons and neutrons in the nucleus? The magnitude of magnetic dipole is inversely
proportional to the mass of the particle. Therefore, for proton, it would be about 2000 times
smaller. Later, Frisch, Eastermann and Stern measured this small magnetic dipole moment to
distinguish it from that of electron spin.

ELECTRON SPIN

The idea of spinning electron was first introduced by Unhlenbeck and Goudsmit (1925).
To explain the multiplet structure (fine structure) of spectral lines, they found it necessary to
assume that electron must have another angular momentum, in addition to the orbital one, of

1 h
value equal to . This angular momentum is referred to as spin angular momentum or spin of
2 2π

1
the electron and is specified by the spin quantum number s= . They also proposed that the spin
2
angular momentum vector ⃗S is similar to the orbital angular momentum vector ⃗
L and can have
(2 s +1) values +ℏ /2 and −ℏ /2. The magnetic spin quantum number m s can thus have the values

1
± . The spin angular momentum vector ⃗S has the magnitude
2

1 1 3 3
|⃗S|=√ s (s+1)ℏ=
√(
2 2
+1 ℏ=
4
ℏ= √ ℏ.
) 2 √
1
The energy of the two atomic states corresponding to m s - values ± will be degenerate.
2

+1
The atom, when placed in a magnetic field, say along z-direction, the states for m s = and
2

−1 +1
ms = will split into two distinct states. The m s = state is known as “the spin up” state and
2 2

−1
the m s = state is known as “the spin down” state.
2

The magnetic moment associated with spin angular momentum ⃗S is given by

−e ⃗ eℏ ⃗S ⃗S
⃗μs =
m
S =−2 ∙ ( )
∙ =−2 ∙ μ B ∙
2m ℏ ℏ
…(2.14)

L, the corresponding relation is

For orbital angular momentum ⃗

−e ⃗ eℏ ⃗L L
⃗
⃗μl=
2m
L=− ( )
∙ =−μ B ∙
2m ℏ ℏ
…(2.15)

We now introduce a new quantity – the gyromagnetic ratio, g. The numerical factor that relates
the magnetic moment in units of Bohr magneton to angular momentum vector in units of ℏ is
called gyromagnetic ratio, g. Corresponding to spin, we thus have gs , and corresponding to the
orbital angular momentum, we have gl .

From equations (2.14) and (2.15), we get

⃗S
μ⃗ s =−gs ∙ μ B ∙ …(2.16)
ℏ
 L
⃗
μ⃗ l=−g l ∙ μB ∙ …(2.17)
ℏ
So that we have plainly gl=1 and gs =2.

Pauli in 1920 first suggested the existence of the fourth quantum number over and above
n, l, m l, without however any explanation for its significance. This was followed, in 1922, by
Stern-Gerlach’s experiment who demonstrated unambiguously the existence of another angular
momentum in addition to the orbital one of the electron.

The above values of μs and S may be obtained from the relativistic quantum mechanical
theory of electron by Dirac.

VECTOR ATOM MODEL

The space quantization and the introduction of the concept of spin led to the vector model of the
atom. First, we shall discuss the method how the two momenta combine and how that brings
changes in spectral characteristics of a one-electron atom.

The orbital angular momentum L

⃗ and the spin angular momentum S⃗ of the electron in an atom
combine to give a total angular momentum, ⃗j . According to the vector model of atom, ⃗J is the
L and ⃗S.
vector sum of ⃗

⃗j =⃗L+ ⃗S
…(2.16)
The magnitude of ⃗j , like those of L
⃗ and S⃗ , is given by

J=|⃗j|=√ j( j+1) ℏ …(2.16)

Where j is the total angular momentum quantum number.

We may write, in analogy with the components L z and S z, the possible J z values:

J z=m j ℏ
…(2.16)

Where m j can take up (2 j+1) values from − j to + j in steps of unity,

i.e. – j, − j+1, − j+2, − j+3,……………………., j −1, j.

In addition ⃗S to ⃗
L, they can be added either parallel or antiparallel.

The total angular momentum quantum number for single electron can have values

j=(l+ s) , j=( l+ s ) …(2.16)

( 12 ) ,
j= l+ ( 12 )(∵ s= 12 )
j= l− …(2.16)

1
In case, l=0, j can have only the value
2

1 3 1
If l=1, j=1± = ∨
2 2 2

1 5 3
If l=2, j=2± = ∨
2 2 2
Since both L
⃗ and S
⃗ show space quantization, ⃗J will also expectedly show space quantization.

L and the ⃗S to precess about ⃗J . In an internal field Be,

The internal magnetic field causes the ⃗
Be. The precession of ⃗
however, ⃗J will precess about⃗ L and ⃗S about the precessing ⃗J is rather very
complicated.

L and ⃗S –
Angle between ⃗

We have ⃗j ¿ ⃗L + ⃗S

⟹ ⃗j ∙ ⃗j ¿ ( ⃗L + ⃗S ) ∙ ( ⃗
L + ⃗S )

⟹ 2 2
|⃗j|2 ¿|⃗L| +|⃗S| + 2 ⃗L ∙ ⃗S
⟹ L ∙ ⃗S ¿|⃗j|2−|⃗
⃗ 2
L| −|⃗S|
2

|⃗j|2−|⃗L|2−|⃗S|2
⟹ cos θ ¿
2|⃗
L||⃗S|
where θ is the angle between the two vectors ⃗
L and ⃗S.

Now since |⃗j|2= j( j+1) ℏ2, |⃗ 2 2

L| =l( l+1) ℏ2 and |⃗S| =s (s+1)ℏ 2
 j( j+1)−l (l+1)−s( s+1)
∴ cos θ ¿ 2 √ l(l+1) √ s (s+1)
Angle between ⃗j and ⃗S –

We have ⃗j ¿ ⃗L + ⃗S ⇒ ⃗L= ⃗j−⃗S

⟹ L ¿ ( ⃗J − ⃗S ) ∙ ( ⃗J + ⃗S )
L∙⃗
⃗

⟹ 2 2 2
|⃗L| ¿|⃗J| +|⃗S| −2 ⃗J ∙ ⃗S
⟹ ⃗J ∙ ⃗S ¿|⃗j|2+|⃗S|2−|⃗
L|
2

2 2 2
|⃗j| +|⃗S| −|⃗L|
⟹ cos θ ¿
2|⃗J||⃗S|
where θ is the angle between the two vectors ⃗J and ⃗S.

Now since |⃗j|2= j( j+1) ℏ2, |⃗ 2 2

L| =l( l+1) ℏ2 and |⃗S| =s (s+1)ℏ 2

j ( j+1 ) +s (s+1)−l (l+1)

∴ cos θ ¿ 2 √ j( j+ 1) √ s (s +1)
Angle between ⃗j and ⃗
L–

We have ⃗j ¿ ⃗L + ⃗S ⇒ ⃗S = ⃗j− ⃗
L

⟹ ⃗S ∙ ⃗S ¿ ( ⃗J − ⃗
L ) ∙ ( ⃗J −⃗L )

⟹ 2 2
|⃗S|2 ¿|⃗J| +|⃗L| −2 ⃗J ∙ ⃗L
2 2 2
⟹ 2 ⃗J ∙ ⃗L ¿|⃗j| +|⃗L| −|⃗S|

|⃗j|2 +|⃗L|2−|⃗S|2
¿
⟹ cos θ 2|⃗J||⃗
L|
where θ is the angle between the two vectors ⃗J and ⃗
L.

Now since |⃗j|2= j( j+1) ℏ2, |⃗ 2 2

L| =l( l+1) ℏ2 and |⃗S| =s (s+1)ℏ 2

j ( j+1 ) +l(l+ 1)−s (s +1)

∴ cos θ ¿ 2 √ j( j+1) √ l(l+ 1)
Spectroscopic terms and their notations