Applied Magnetic Field
Weak (< 1T) Strong (>1T)
ZEEMAN EFFECT Paschen Back Effect
Normal Zeeman Effect Anomalous Zeeman Effect
•Weak Fields (Zeeman Effect): The coupling between the orbital (L) and spin (S) angular momenta is stronger
than their coupling to the external magnetic field. The total angular momentum (J = L + S) precesses around
the field direction.
•Strong Fields (Paschen-Back Effect): The magnetic field becomes strong enough to disrupt the L-S
coupling. The orbital and spin angular momenta now couple more strongly to the magnetic field than to each
other, and they precess independently around the field direction.
Zeeman Effect Paschen Back Effect
Zeeman Effect
When a light source is placed in a weak magnetic field , then the spectral lines split into its components, this effect is known as zeeman
effect and the number of components are called as Zeeman components. (Weak magnetic field B≤1Tsela (T))
Splitting of spectral lines in presence of weak mag. Field in called Zeeman effect. Ref: https://www.youtube.com/watch?v=SRTP-Obia0w&t=1s
Types of Zeeman effect:
1) Normal Seeman effect
2) Anomalous Zeeman effect
Note: Zeeman splitting is smaller than fine structure splitting
Normal Zeeman effect:
The normal Zeeman effect is be observed in elements having paired electrons (closed subshells) with resultant
spin quantum number equal to zero (S=0).
• S = 0 ⇒ Total angular momentum vector J = Orbital angular momentum vector L (for normal Zeeman effect)
• Also S = 0 ⇒ Multiplicity (M)= 2S+1=1 Implying that, Normal Zeeman effect is observed in only singlet to
singlet transitions.
• 𝑀𝐿 = 𝑀𝐽 (𝑀𝑠 = 0) Hence, Normal Zeeman effect can be explained without considering electron spin.
• When an atom is placed in a weak external magnetic field B say along Z direction) then vector L precesses
around the fiels direction Z. With its quantized component along z direction given by: 𝐿𝑧 = 𝑀𝐿 ℏ
• where, 𝑀𝐿 = L to –L (difference of 1) each L level split into 2L+1 levels (quantization of L due to application of
external mag field). This precession is Larmor precession.
|orbital magnitic moment vector𝜇𝐿 | 𝑒
• Angular velocity of this precession = 𝜔𝐿 = B = 2𝑚 B
|orbital angular momentum vector L|
𝜇𝐿 𝑒
• Here = is gyromagnetic ratio of orbital motion of electrons
L 2𝑚
• This precession is Larmor precession.
|orbital magnitic moment vector𝜇𝐿 | 𝑒
• Angular velocity of this precession = 𝜔𝐿 = B = 2𝑚 B
|orbital angular momentum vector L|
𝜇𝐿 𝑒
• Here
L
= 2𝑚 is gyromagnetic ratio of orbital motion of electrons
𝑒
• Interaction energy of such precession 𝛥𝐸 = 𝜔𝐿𝑧 = 2𝑚 B 𝑀𝐿 ℏ =𝑀𝐿 𝜇𝐵 B ℎ𝑒𝑟𝑒, 𝜇𝐵 = Bohr magneton
𝛥𝐸 𝑒𝐵
• Term value −𝛥𝑇 =
ℎ𝑐
=
4𝜋𝑚𝑐
𝑀𝐿 = 𝑀𝐿 L’= 𝒈𝑳 𝑀𝐿 L’ where, 𝒈𝑳 =lande g factor =1 (here) −𝜟T = 𝒈𝑳 𝑴𝑳 L’
• L’ = wave number separation between any two consecutive Zeeman levels called Lorentz unit or in other words
• Lorentz unit gives the splitting between the Zeeman components.
𝒆𝑩 𝒆
• L’= =( )×B = (46.7 ×B) 𝒎−𝟏
𝟒𝝅𝒎𝒄 𝟒𝝅𝒎𝒄
𝐽 𝐽+1 −𝐿 𝐿+1 +𝑆(𝑆+1)
• Note: Remember that Lande g-factor =1+
2𝐽(𝐽+1)
• Example: *MCQs
• Let us consider the transition 1D2 → 1P1
• Here, (L=2, 1)⇒ 𝑀𝐿 = -L to +L gives (2L+1) values respectively giving 5 and 3 equal spaced
components
• The selectin rule ∆𝑴𝑳 = 𝟎, ±𝟏 allows 9 transitions but all the transition for same ∆𝑀𝐿 will
coincide in same wave number.
• ∆𝑀𝐿 = 0 gives 𝜋 component in field free line (or no filed applied line)
• ∆𝑀𝐿 = ±1 gives two symmetrically displaced 𝜎 components.
𝒆𝑩
• Wave number separation between consecutive levels ∆ 𝜈= L’=(𝜇𝐵 B)/hc = = 46.7 B 𝒎−𝟏 /𝑻
𝟒𝝅𝒎𝒄
• that is, energy difference between consequtive lines= ± 𝜇𝐵 B
• Frequency difference between consecutive lines = 𝜇𝐵 B/h
• Polarization Rules: Important for numericals
• When Observed at 90𝑜 to the field,
• Transition ∆𝑀𝐿 = 0 E vector parallel to field ⇒ 𝜋 component
• Transition ∆𝑀𝐿 = ±1 , E vector perpendicular to field ⇒ 𝜎 component
• Intensity Ratio:
• Both 𝜎 components together have same intensity as the 𝜋 component.
Anomalous Zeeman effect:
It arises for spectral lines in which initial and final states have nonzero spin (S ≠0)
⇒ J ≠0 and 𝜇𝐽 ≠0
𝒆
Interaction energy 𝚫𝑬 = 𝝎𝑳𝒛 = 𝑔𝐽 B 𝑀𝐽 ℏ = 𝑔𝐽 𝑀𝐽 𝜇𝐵 B
𝟐𝒎
𝚫𝑬 𝒆𝑩
−𝚫𝑻 = = 𝑔𝐽 𝑀𝐽 = 𝑔𝐽 𝑀𝐽 L’
ℎ𝑐 𝟒𝝅𝒎𝒄
This is expression for weak mag field interaction energy of Zeenam shift.
Each J level slit into 2J+1 equispaced Zeeman levels for all possible value of 𝑀𝐽 .
Ex 2P1/2 → 2S1/2 ⇒ D1 line of sodium
−𝜟T = 𝒈𝑳 𝑴𝑳 L’
2P → 2S
3/2 1/2 ⇒ D2 line of sodium
Intensity rules:
Paschen Back Effect
In Zeeman effect the external magnetic field is weak as compared with the internal fields due to spin and orbital motion of valance electrons.
When however the strength of external field is increased the separartion between the Zeeman components increase until they become greater
than the separation between the multiplets fine structure components.
The anomalous zeeman pattern then changes over to the normal zeeman pattern. This is known as Paschen back effects.
When the external field B becomes stronger than internal fields, the magnetic coupling between J
and B exceeds that between L and S and the precession of J around B becomes faster than that of L
and S around J.
Thus coupling between L ans S breaks and J is no longer fixed in magnitude.
As B increases L and S start to precess around B with their components Lz and Sz in direction of B.
|Lz|= 𝑀𝐿 ℏ where, 𝑀𝐿 = -L to +L and
1 1
|Sz|= 𝑀𝑠 ℏ where, 𝑀𝑠 = - to +
2 2
𝑒 𝑒
𝜔𝐿 =
2𝑚
B 𝜔𝑠 =2 B
2𝑚
−𝜟T = (𝑴𝑳 +2 𝑴𝒔 ) L’
Interaction energy
𝑒
𝛥𝐸𝐿 = 𝜔𝐿 𝐿𝑧 = B 𝑀𝐿 ℏ =𝑀𝐿 𝜇𝐵 B
2𝑚
𝑒
𝛥𝐸𝑠 = 𝜔𝑠 𝑆𝑧 = 2 2𝑚 B 𝑀𝑠 ℏ =2𝑀𝑠 𝜇𝐵 B
𝛥E = 𝛥𝐸𝐿 + 𝛥𝐸𝑠
𝛥𝐸 𝑒𝐵
-𝛥T= ℎ𝑐 = (𝑀𝐿 +2 𝑀𝑠 ) 4𝜋𝑚𝑐
Or, -𝜟T = (𝑴𝑳 +2 𝑴𝒔 ) L’
Spin orbit correction: -𝛥T = (𝑀𝐿 +2 𝑀𝑠 ) L’+ a 𝑀𝐿 𝑀𝑠
Example:
Transition From Weak to Strong Field
“The number of magnetic levels into which a given state splits does not depend on field strength but the amount of
splitting does”
In weak field a level with inner qt. no. J split into (2J+1) levels.
1 1
For one valance electron system J can have L+ 2 and L− 2 .
1 1
So that a level is split into {2(L+ 2 )+1}+ {2(L− 2 )+1} = 4L+2 levels
In strong field L alone has 2L+1 orientations and S has 2S+1, together giving
(2L+1)(2S+1)=4L+2 levels (Put S=1/2)
In weak field each magnetic level is identified by quantum numbers J and 𝑀𝐽 , while in a strong field the characteristic
quantum numbers are 𝑀𝑠 and 𝑀𝐿 .
Now how on changing the B the level change???
One thing is sure that sum of projection angular momentum vectors does not change…
This implies the rules are:
(1) 𝑴𝑱 = 𝑴𝒔 + 𝑴𝑳
(2) No two levels with same 𝑴𝑱 cross each other
Transition of magnetic levels corresponding to states:
