B.Sc.

V Semester (P-6) Elements of Atomic, Molecular & Laser Physics A D B F G College, H Halli
Physics, Semester-V
DSC 6: Elements of Atomic, Molecular & Laser Physics
Unit 2: Vector atom Model and Optical Spectra
Vector atom model – model fundamentals, spatial quantisation, spinning electron; Quantum numbers
associated with vector atomic model; Coupling schemes – L-S and j-j schemes; Pauli’s exclusion principle;
Magnetic dipole moment due to orbital motion of electron – derivation; Magnetic dipole moment due to spin
motion of electron; Lande g-factor and its calculation for different states; Stern-Gerlach experiment –
Experimental arrangement and Principle; Fine structure of spectral lines with examples; Spin-orbit
coupling/Spin-Orbit Interaction – qualitative; Optical spectra – spectral terms, spectral notations, selection
rules, intensity rules; Fine structure of the sodium D-line; Zeeman effect: Types, Experimental study and
classical theory of normal Zeeman effect, Zeeman shift expression (no derivation), examples; Stark effect:
Experimental study, Types and examples.

Vector Atom Model

Bohr’s theory was able to explain only the series spectra of the simplest hydrogen atom. It could not explain
the multiple structure of spectral lines in the simplest hydrogen atom. Sommerfeld’s theory was able to give
an explanation of the fine structure of the spectral lines hydrogen. However, Sommerfeld’s theory could not
predict the correct number of the fine structure lines.

These theories were inadequate to explain new discoveries like Zeeman Effect and Stark Effect in which the
spectral lines could be split up under the influence of magnetic and electric fields.

Another drawback of the Bohr model was that it could not explain how the orbital electrons in atoms were
distributed around the nucleus.

Therefore, in order to explain the complex spectra of atoms and their relation to atomic structure, the vector
atom model was introduced. The two distinct features of the vector atom model are the concept of Space
quantization and spinning electron hypothesis.

Space Quantization: According to Bohr’s theory, the orbits are quantized as regards their magnitude only.
But according to quantum theory, the orientation of the orbits in space also should be quantized. To specify
the orientation of the electron orbit in space, we need a fixed reference axis. This reference line is chosen as
the direction of an external magnetic field that is applied to the atom. The different permitted orientations of
an electron orbit are determined by the fact that the projection of the quantized orbit on the field direction
must themselves be quantized. The idea of space quantization leads to an explanation of Zeeman Effect. The
Stern-Garlach experiment provided an excellent proof of the space quantization of atom.

Spinning electron: The concept of spinning electron was introduced by Uhlenbeck and Goudsmit in 1926.
According to their hypothesis, the electron spins about an axis of its own, while it also moves round the nucleus
of the atom in its orbit. According to the quantum theory, the spin of the electron also should be quantized.
B.Sc. V Semester (P-6) Elements of Atomic, Molecular & Laser Physics A D B F G College, H Halli
Since the orbital and spin motions are both quantized in magnitude and direction, they are considered as
quantized vectors. Hence the atom model based on these quantized vectors is called the ‘vector atom model’,
to which vector laws apply.

Magnetic dipole moment due to orbital motion of the electron:

Consider an electron moving in an elliptical orbit of area A with a period

T. The electron crosses any point in the orbit 1/𝑇 times in unit time. This
is equivalent to a current (𝑖 = 𝑒/𝑇) in a loop of area A, where e is the
charge of the electron. Applying ampere’s theorem, this current gives rise
to a magnetic dipole moment given by

𝑒𝐴
𝜇𝑙 = 𝑖𝐴 = … … … … (1)
𝑇
1 𝑑𝜑
Since the total areal velocity in a central orbit is . 𝑟2 , the area
2 𝑑𝑡

𝑇
1 2 𝑑𝜑
𝐴=∫ . 𝑟 . ( ) . 𝑑𝑡
0 2 𝑑𝑡

Now, the angular momentum of the electron

𝑑𝜑
𝐿 = 𝑚𝑟 2 𝐿 = 𝑚𝑟 2 𝜔
𝑑𝑡

𝑑𝜑 𝐿
𝑟2 =
𝑑𝑡 𝑚

1 2 𝑑𝜑 𝐿
.𝑟 . =
2 𝑑𝑡 2𝑚
𝑇
𝐿 𝐿𝑇
∴𝐴=∫ . 𝑑𝑡 = … … … … (2)
0 2𝑚 2𝑚

Substituting the value of A in equation 1,

𝑒 𝐿𝑇
𝜇𝑙 = .
𝑇 2𝑚
𝑒
𝜇𝑙 = .𝐿
2𝑚

Since the angular momentum is quantized, we have𝐿 = 𝑙ħ

𝑒
𝜇𝑙 = . 𝑙ħ
2𝑚

𝑒ℎ ℎ
𝜇𝑙 = .𝑙 ∵ (ℏ = )
4𝜋𝑚 2𝜋
B.Sc. V Semester (P-6) Elements of Atomic, Molecular & Laser Physics A D B F G College, H Halli
𝑒ħ
From the above equation it is clear that, 𝜇𝑙 is directly proportional to 𝑙. is the smallest unit of magnetic
2𝑚

dipole moment and is called the Bohr magneton and is denoted by 𝜇𝐵

𝑒ℎ (1.602 × 10−19 ) × (6.626 × 10−34 )

𝜇𝐵 = = = 9.272 × 10−24 𝐽𝑇 −1
4𝜋𝑚 4 × 3.142 × 9.109 × 10−31

Magnetic Dipole Moment Due to Spin:

An electron spinning about its axis should also behave as a tiny magnet and possess a magnetic dipole moment
due to this spin. However, nothing is known about the shape of an electron or the manner in which its charge
is distributed. Hence it is impossible to calculate its spin magnetic dipole moment in a manner analogous to
that used for the orbital motion. In order to obtain agreement with experimental results, the spin magnetic
dipole moment (μs) is assigned the value,
𝑒
𝜇𝑠 = 2. .𝑃
2𝑚 𝑠

𝑃𝑠 = 𝑠ℏ

𝑒
𝜇𝑠 = 2. . 𝑠ℏ
2𝑚

𝒆𝒉
𝝁𝒔 = 𝟐. .𝒔
𝟒𝝅𝒎

The Stern and Gerlach Experiment:

The direct evidence for the existence of magnetic moments of atoms and their space quantization is
provided by the experiments of Stern and Gerlach.

The experiment is based on the behaviour of a magnetic dipole in a non-uniform magnetic field. In a
uniform magnetic field, the dipole experiences a torque that tends to align the dipole parallel to the field. If
the dipole moves in such a field in a direction normal to the field, it will trace a straight line path without any
deviation.

In an inhomogeneous magnetic field, the dipole experiences, in addition, a translatory force. If the
atomic magnet flies across such an inhomogeneous magnetic field normal to the field direction, it will be
deviated away from its rectilinear path. An expression for the deviation produced may be obtained as follows.

𝑑𝐵
Let the magnetic field vary along the X-direction, so that the field gradient is and is positive (fig).
𝑑𝑥

CD is the atomic magnet of pole strength p, length l, and dipole moment 𝜇, with its axis inclined at an angle
𝜃 to the field direction. If the field strength at the pole C is B, then the field strength at the other pole D will
𝑑𝐵 𝑑𝐵
be𝐵 + 𝑑𝑥 𝑙 cos 𝜃. Hence the forces on the two poles are 𝑝𝐵and 𝑝 [𝐵 + 𝑑𝑥 𝑙 cos 𝜃]. Hence the atomic magnet
𝑑𝐵
experiences not only a torque but also a translator force Fx= 𝑑𝑥 𝑝𝑙 cos 𝜃.
B.Sc. V Semester (P-6) Elements of Atomic, Molecular & Laser Physics A D B F G College, H Halli
The time taken by the atom to travel
through the field is

𝐿
𝑡=
𝑉

Where, 𝐿 = length of the path of the atom

in the field &

𝑉 = velocity of the atomic magnet.

The acceleration given to the atom along the field direction by the translatory force is

𝐹𝑥
𝑎=
𝑚
The displacement of the atom along the field direction on emerging out of the field is

1
𝛼 = 𝑎𝑡 2
2

1 𝐹𝑥 𝐿2
𝛼= . . 2
2 𝑚 𝑉

1 𝑑𝐵 𝜇𝑠 cos 𝜃 𝐿2
𝛼= . . . 2
2 𝑑𝑥 𝑚 𝑉

1 𝑑𝐵 𝜇 𝐿2
𝛼= . . .
2 𝑑𝑥 𝑚 𝑉 2
Experimental Arrangement:

Silver is boiled in an oven (fig 1). Atoms of silver stream out from an opening in the oven. By the use of slits
S1& S2, a sharp linear beam of atoms is obtained. These atoms then pass through a very inhomogeneous
magnetic field between the shaped poles of a magnet M M. A high degree of non-uniformity in the magnetic
field is produced by making one of the pole pieces of a powerful electromagnet a knife-edge shape (Fig 2).
The lines of force are close together at the knife edge and the field there is much stronger than that at the other
B.Sc. V Semester (P-6) Elements of Atomic, Molecular & Laser Physics A D B F G College, H Halli
pole piece. The magnetic field is at right angles to the direction of movement of the atoms. Finally the atoms
fall on a photographic plate P. The whole arrangement is enclosed in an evacuated chamber.

With no field, the beam produces a narrow continuous line on the plate (Fig 3). In terms of the vector
atom model, those atoms, with electron spins directed parallel to the magnetic field, will experience a force in
one direction, whereas those with oppositely directed spins will experience a force in the opposite direction.
According to this, the beam of atoms should split into two beams in its passage through the inhomogeneous
magnetic field. This splitting of the beam into two parts of approximately equal intensity was actually observed
in these experiments. On applying the inhomogeneous magnetic field, it was found that the stream of silver
atoms splits into two separate lines (Fig 3). Knowing, dB/dx, L, V and 𝛼, 𝜇 was calculated. It was found that
each silver atom had a magnetic moment of one Bohr magneton in the direction of the field.
Quantum Numbers associated with Vector Atom Model:
There are seven quantum numbers associated with the vector atom model, namely
1. The principal quantum number (n)
2. The orbital quantum number (l)
3. The spin quantum number (s)
4. Total angular momentum quantum number (j)
5. Magnetic orbital quantum number (ml)
6. Magnetic spin quantum number (ms)
7. Magnetic total angular momentum quantum number (mj)

The Principal Quantum Number (n): This quantum number represents the main shells of the atom. The
serial number of the shells starting from the innermost is designated as its principal quantum number. It can
take only integral values excluding zero. i.e., n = 1, 2, 3, 4,…..(K, L, M,……..)

The Orbital Quantum Number (l): This quantum number represents the sub shells of the atom. This may
take any integral value from 0 to (𝑛 − 1).

Example:

If 𝑛 = 1, 𝑙 can take only one values 0

If 𝑛 = 2, 𝑙 can take two values 0, 1

If 𝑛 = 3, 𝑙 can take three values 0, 1, 2

By convention, an electron for which 𝑙 = 0, is called 𝑠 electrons; if 𝑙 = 1, 𝑝 electrons; 𝑙 = 2, 𝑑 electrons;

𝑙 = 3, 𝑓 electrons etc.

The orbital angular momentum 𝑝𝑙 of the electron is given by 𝑝𝑙 = 𝑙ℏ

According to wave mechanics, 𝑝𝑙 = √𝑙(𝑙 + 1). ℏ

B.Sc. V Semester (P-6) Elements of Atomic, Molecular & Laser Physics A D B F G College, H Halli
1
The Spin Quantum Number (s): This has only one value, = 2

The spin angular momentum 𝑝𝑠 of the electron is given by 𝑝𝑠 = 𝑠ℏ

According to wave mechanics, 𝑝𝑠 = √𝑠(𝑠 + 1). ℏ

Total Angular Momentum Quantum Number (j):

It represents the total angular momentum of the electron which

is the sum of the orbital angular momentum and spin angular
momentum. It is represented by the vector j and is defined by
the equation 𝑗⃗ = 𝑙⃗ + 𝑠⃗ with the restriction that 𝑗⃗ is positive. The
1
spin angular momentum 𝑠 = ± 2. Therefore 𝑗⃗ = 𝑙⃗ ± 𝑠⃗, plus sign when 𝑠 is parallel to 𝑙 and minus sign when

𝑠 is antiparallel to 𝑙.

5 3
Example: If 𝑙 = 2, 𝑡ℎ𝑒𝑛 𝑗 𝑐𝑎𝑛 𝑡𝑎𝑘𝑒 𝑡𝑤𝑜 𝑣𝑎𝑙𝑢𝑒𝑠, 2 𝑜𝑟 2 (fig).

The total angular momentum𝑝𝑗 of the electron is given by 𝑝𝑗 = 𝑗ℏ

According to wave mechanics, 𝑝𝑗 = √𝑗(𝑗 + 1). ℏ

To explain the splitting of spectral lines in a magnetic field, three more magnetic quantum numbers
are introduced.

Magnetic Orbital Quantum Number (𝒎𝒍 ) The projection of the orbital quantum
number 𝑙 on the magnetic field direction is called the magnetic orbital quantum number
𝑚𝑙 . The possible values of 𝑚𝑙 are −𝑙, 0, +𝑙. That is there are (2𝑙 + 1) possible values of
𝑚𝑙 .

Example:

1. If 𝑙 = 3, 𝑚𝑙 can take 7 values, -3, -2, -1, 0, +1, +2, +3, the orientations are as in
the figure (1).
2. If 𝑙 = 4, 𝑚𝑙 can take 9 values, -4, -3, -2, -1, 0, +1, +2, +3, +4

Magnetic Spin Quantum Number (𝒎𝒔 ): This is the projection of the spin vector 𝑠 along the direction of the
magnetic field. 𝑚𝑠 can have only two possible positions with respect to the magnetic field
1 1
it may be parallel to it or antiparallel. Thus 𝑚𝑠 can have only two values + 2 𝑜𝑟 − 2

Magnetic Total Angular Momentum Quantum Number (𝒎𝒋 ):

This is the projection of total angular momentum vector 𝑗 on the direction of the magnetic
field. 𝑚𝑗 can have (2𝑗 + 1) values from +𝑗 𝑡𝑜 − 𝑗 excluding zero.
B.Sc. V Semester (P-6) Elements of Atomic, Molecular & Laser Physics A D B F G College, H Halli
3 3 1 1 3
Example: If 𝑗 = 2, 𝑚𝑗 can take 4 value, + 2 , + 2 , − 2 , − 2, the orientations are as in the figure.(2).

The Pauli Exclusion Principle:

The four quantum numbers 𝑛, 𝑙, 𝑚𝑙 , 𝑎𝑛𝑑 𝑚𝑠 determine the state of an electron completely. Thus Pauli
formulated a principle and according to it “No two electrons in an isolated atom may have the same four
quantum numbers”.

The principle implies that each electron in an atom must have a different set of quantum numbers
𝑛, 𝑙, 𝑚𝑙 , 𝑎𝑛𝑑 𝑚𝑠 . If two electrons have all their quantum numbers identical, then one of those two electrons
would be excluded from entering into the constitution of the atom. Hence the name ‘exclusion principle’.

This principle enables us to calculate the number of electrons that can occupy a given subshell.

1. Consider K shell with 𝑛 = 1

Number of
𝑛 𝑙 𝑚𝑙 𝑚𝑠 Subshell
electrons

1
1 0 0 + 1
2
s
1
0 0 − 1
1 2

Hence the K shell can have two electrons that is K shell is completed with two electrons.

2. Consider L shell with 𝑛 = 2

Number of
𝑛 𝑙 𝑚𝑙 𝑚𝑠 Subshell
electrons
1
2 0 0 ± 2 s
2
1
2 1 +1 ± 2
2
1
2 1 0 ± 2 p
2
1
1 -1 ± 2
2 2

For L shell there are two subshells, they are (𝑛 = 2, 𝑙 = 0) with 2 electrons and (𝑛 = 2, 𝑙 = 1) with 6
maximum electrons as shown in the above table. Thus L-shell with two subshells is therefore completed when
it contains 2+6=8 electrons.

3. Consider M shell with 𝑛 = 3

Number of
𝑛 𝑙 𝑚𝑙 𝑚𝑠 Subshell
electrons
3 0 0 ±1/2 2 s
B.Sc. V Semester (P-6) Elements of Atomic, Molecular & Laser Physics A D B F G College, H Halli
3 1 -1 ±1/2 2

3 1 0 ±1/2 2 p

3 1 +1 ±1/2 2

3 2 -2 ±1/2 2

3 2 -1 ±1/2 2

3 2 0 ±1/2 2 d

3 2 +1 ±1/2 2

3 2 +2 ±1/2 2

The first and second subshells are completed by 2 and 6 electrons as explained above. The third

subshell is completed with 2(2𝑙 + 1), that is, 10 electrons since 𝑙 = 2.hence the total number of

electrons require to complete the M-shell is 18.

In general, we get the two following conclusions:

i. In the nth shell there are n sub-shells corresponding to the values 0, 1, 2, …….(n-1) of 𝑙.

The maximum number of electrons in a sub shell with a given value of 𝑙 is 2(2𝑙 + 1),

Orbital quantum number(𝑙) Number of possible electron states Subshell symbol

0 2 𝑠
1 6 𝑝
2 10 𝑑
3 14 𝑓
4 18 𝑔

ii. The maximum number of electrons (X) that can be accommodated in a shell with principal
quantum number 𝑛 is
𝑛 = 𝑠𝑢𝑚 𝑜𝑓 𝑡ℎ𝑒 𝑒𝑙𝑒𝑐𝑡𝑟𝑜𝑛𝑠 𝑖𝑛 𝑡ℎ𝑒 𝑐𝑜𝑛𝑠𝑡𝑖𝑡𝑢𝑒𝑛𝑡 𝑛 𝑠𝑢𝑏𝑠ℎ𝑒𝑙𝑙𝑠

𝑙=(𝑛−1)

𝑋 = ∑ 2(2𝑙 + 1)
𝑙=0

𝑙=(𝑛−1)

𝑋 = 2 ∑ (2𝑙 + 1)
𝑙=0

𝑋 = 2[1 + 3 + 5 + ⋯ … … … … . +{2(𝑛 − 1) + 1}
B.Sc. V Semester (P-6) Elements of Atomic, Molecular & Laser Physics A D B F G College, H Halli
𝑎+𝑙
The above sum is an arithmetic progression whose sum is given by the formula𝑛 ( ), where 𝑎 is the 1st term
2

and 𝑙 is the last term.

1 + 2(𝑛 − 1) + 1
∴ 𝑋 = 2 [𝑛 { }]
2

2 + 2𝑛 − 2
𝑋 = 2 [𝑛 { }]
2

𝑋 = 2𝑛2

Electronic configuration of atoms:

Carbon – C (6): 1𝑠 2 , 2𝑠 2 , 2𝑝2

Neon – Ne (10): 1𝑠 2 , 2𝑠 2 , 2𝑝6

Aluminum – Al (13): 1𝑠 2 , 2𝑠 2 , 2𝑝6 , 3𝑠 2 , 3𝑝1

Potassium – K (19): 1𝑠 2 , 2𝑠 2 , 2𝑝6 , 3𝑠 2 , 3𝑝6 , 4𝑠1

Chromium – Cr (24): 1𝑠 2 , 2𝑠 2 , 2𝑝6 , 3𝑠 2 , 3𝑝6 , 3𝑑 5 , 4𝑠1

Cobalt – Co (27): 1𝑠 2 , 2𝑠 2 , 2𝑝6 , 3𝑠 2 , 3𝑝6 , 4𝑠 2 , 3𝑑 7

Copper – Cu (29): 1𝑠 2 , 2𝑠 2 , 2𝑝6 , 3𝑠 2 , 3𝑝6 , 3𝑑10 , 4𝑠1

Coupling Schemes:

There are several ways in which the different vectors of the electrons may combine to give the vector
representing the atom as a whole. The method of combination depends on the interaction or coupling between
the component vectors, since the orbital and spin motions of the electron produce magnetic fields and thereby
result in mutual perturbation. It is usual to distinguish two types of combination known as the L – S coupling
and j – j coupling.

L – S Coupling:

This coupling is the one which occurs most frequently and hence is known as the normal coupling. In
this type the several spin vectors of the electrons combine to form a resultant vector S. similarly several orbital
vectors combine to form resultant vector L, then the S and L combine to make the vector J, which represents
the total angular momentum of the atom. The process may be symbolically represented as

(𝑠1 + 𝑠2 + 𝑠3 + − − − − −) + (𝑙1 + 𝑙2 + 𝑙3 + − − − − −) = 𝐿 + 𝑆 = 𝐽
B.Sc. V Semester (P-6) Elements of Atomic, Molecular & Laser Physics A D B F G College, H Halli

This sort of coupling is the most natural one when the interaction between the individual spins on the one hand
and the individual orbital moments on the other are very strong (Fig 1).

The j – j Coupling:

Under certain circumstances, the interaction between the spin and orbital vectors in each electron may be
stronger than that between either the spin vectors or the orbital vectors of the different electrons. If this is the
case, each electron is considered separately and its contribution to the total angular momentum of the atom is
obtained by combining first its individual spin and orbital vector using the relation 𝑗 = 𝑙 + 𝑠. The vector sum
of all the individual 𝑗 vectors of the different electrons thus gives the total angular momentum 𝐽 of the atom
(Fig 2). This sort of coupling may be symbolically represented as

[(𝑠1 + 𝑙1 ) + (𝑠2 + 𝑙2 ) + − − − − −] = [𝑗1 + 𝑗2 + 𝑗3 + − − − − −] = 𝐽

The valence electrons of an atom determine the chemical and optical properties of their atoms. The electrons
in the closed inner orbits do not take part in the emission of spectral lines.
Spin – Orbit Interaction:

The fine structure doubling of spectral lines may be

explained on the basis of a magnetic interaction
between the spin and orbital angular momenta of
atomic electrons. In its orbital motion the electron goes
in a closed path round the nucleus of charge Ze. When
viewed from the electron, it is equivalent to the nucleus
of charge Ze going round the electron in a closed path
(Fig). At the point where the electron is situated, a magnetic induction is produced because of the nucleus
going round in a closed path. The interaction between the electron’s spin magnetic moment and this magnetic
field leads to the phenomenon of spin-orbit coupling.

Optica Spectra

Spectral terms: Atoms are divided into two main categories, namely one electron system and many electron
system.
B.Sc. V Semester (P-6) Elements of Atomic, Molecular & Laser Physics A D B F G College, H Halli
i. The alkali metals such as lithium, sodium and potassium have a single valence electron. The valence
electron in the alkali metals therefore behaves much like the orbiting electron in the hydrogen atom.
Hence the alkali metals have a hydrogen-like spectra. Their spectrum is also referred as the one-
electron spectra.
ii. In the many electrons system, the atoms have more than one valence electron. The alkaline earth
elements belonging to the two-electron system have spectra which are similar among themselves.
Spectral notations: The states of the atom, in which the values of its L vectors are 0, 1, 2, 3, 4, 5 are
represented by the capital letters, S, P, D, F, G, H etc., respectively. The value of the total angular momentum
of the atom J is written as a subscript at the lower right of the letter representing the particular L value of the
atomic state. The multiplicity of the total spin S (2S+1) is written as a superscript at the upper left of the letter.
Examples:
1 3
i. A state with 𝐿 = 1, 𝑆 = 2 𝑎𝑛𝑑 𝐽 = 2 would be written as 2𝑃3/2 and read “doublet P three halves”.

ii. A state with 𝐿 = 2, 𝑆 = 1 𝑎𝑛𝑑 𝐽 = 2 would be written as 3𝐷2 and read “triple D two”.
The Selection rule: An electron cannot jump from one energy level to all other energy levels. A transition of
an electron between two levels is possible only if certain rules called section rules are satisfied. For the vector
atom model, three section rules have been devised.
i. The selection rule for 𝑳 𝑖𝑠 ∆𝐿 = ±1, that is, only those lines are observed for which the value of
𝐿 𝑐ℎ𝑎𝑛𝑔𝑒𝑠 𝑏𝑦 ± 1. For example, L can change from 0 to 1 (∆𝐿 = +1) or from 1 to 0 (∆𝐿 = −1) (S
to P). L cannot change from 0 to 2 (S to D).
ii. The selection rule for 𝑱 𝑖𝑠 ∆𝐽 = ±1 𝑜𝑟 0. But 0 → 0 is excluded.
iii. The selection rule for 𝑺 𝑖𝑠 𝑔𝑖𝑣𝑒𝑛 𝑏𝑦 ∆𝑆 = 0.
Intensity rules: Whether an allowed transition is weak of strong is determined by what are known as intensity
rules. They are,
∆𝐿 = −1 ∆𝐽 = −1 Strongest
∆𝐿 = −1 ∆𝐽 = 0 Less intense
∆𝐿 = +1 ∆𝐽 = +1 Weak
∆𝐿 = +1 ∆𝐽 = 0 Very weak
∆𝐿 = −1 ∆𝐽 = +1
Forbidden
∆𝐿 = +1 ∆𝐽 = −1
Fine structure of the sodium D-line:
Ten out of the eleven electrons of the normal sodium atom are
interlocked in closed shells. They contribute nothing to the
angular momentum of the atom we have to consider only the
states of eleventh optical electron in discussing the spectrum of
neutral sodium.
B.Sc. V Semester (P-6) Elements of Atomic, Molecular & Laser Physics A D B F G College, H Halli
The D-line belongs to principal series. Lines of the principal series are due to transitions from a P state
to the S state. For the upper P state, L=1, J= 3/2 or 1/2. Hence the two possible states are 2𝑃3/2 𝑎𝑛𝑑 2𝑃1/2 . For
the lower S state, L=0, J=1/2, so that only one term 2𝑆1/2 is possible. Figure shows the two possible transitions
between the two terms of the P state and the single term of the S state, they are: (i) 2𝑃1/2 → 2𝑆1/2 which
results in the 𝐷1 line of wavelength 5896 𝐴0 and (ii) 2𝑃3/2 → 2𝑆1/2 giving the 𝐷2 line of wavelength 5890 𝐴0 .
Now applying the selection rules for L and J, both the transitions are allowed. This explains the doublet fine
structure of the sodium D line.
Zeeman Effect:

Zeeman Effect is a magneto-optical phenomenon discovered by Zeeman in 1896. He observed that if a source
of light producing line spectrum is placed in a magnetic field, the spectral lines are split up into two or three
components, it is called Normal Zeeman effect and can be explained quantitatively by classical theory.

The splitting of a spectral line into more than three components in ordinary weak magnetic fields is called
Anomalous Zeeman effect. This cannot be explained by classical theory.

Experimental arrangement for the normal Zeeman Effect.

The arrangement is shown in Fig. M M is an electromagnet capable of producing a very strong magnetic field.
Its conical pole pieces PP have longitudinal holes drilled through them. A source of light (L) emitting line
spectrum (say, a sodium vapour lamp) is placed between the pole-pieces. The spectral lines are observed with
the help of a spectrograph (S) high resolving power. The Zeeman Effect may be observed in two ways.

Longitudinal view:

The position of the spectral line is noted without applying the magnetic field. The magnetic field is
now switched on and the spectral line is viewed longitudinally through the hole drilled in the pole-pieces and
hence parallel to the direction of the field. It is found that the spectral line is split into two components, one
slightly shorter in wavelength and the other slightly longer in wavelength than the original line. The original
line is not present. The two components are found to be symmetrically situated about the position of the parent
line. Analysing the two lines with a Nicol prism, both the lines are found to be circularly polarised in opposite
directions. This is called normal longitudinal Zeeman Effect.
B.Sc. V Semester (P-6) Elements of Atomic, Molecular & Laser Physics A D B F G College, H Halli
Transverse View:

The spectral line is then viewed transversely i.e., perpendicular to the direction of the magnetic field.
In this case, the single spectral line is split up into three components when the magnetic field is applied. The
central line has the same wavelength as the original line and is plane polarised with vibrations parallel to the
field. The outer lines are symmetrically situated on either side of the central line. The displacement of either
outer line from the central line is known as the Zeeman shift. The two outer lines are also plane polarized
having vibrations in a direction perpendicular to the field. This is called Normal transverse Zeeman Effect.

Lorentz classical theory of normal Zeeman effect:

The emission of light by a glowing gas is due to the vibratory motion of the electrons. The electrons in the
atom execute simple harmonic vibration about the centre of the atom. The frequency of the spectral line is
given by the frequency of vibration of the electron. Any linear motion of an electron can be resolved into three
components—a linear motion along the magnetic field and two opposite circular motions perpendicular to the
field. It is known that no mechanical force acts upon a charge when it moves in the direction of the field. So,
the linear motion along the field is not affected by the field and hence the frequency of this component is
unchanged by the magnetic field. The other two circular components are affected by the magnetic field, one
being retarded and the other being accelerated. Hence the frequency of one of these circular components is
increased and that of the other is decreased by the same amount. In the longitudinal view, the unaltered linear
component along the field gives no light waves along the direction of observation due to the transverse nature
of light vibrations. Hence the original line is not observed. The two altered circular components at right angles
to the field produce circularly polarised light waves. This explains the longitudinal Zeeman pattern. In the
transverse view, the unaffected linear component sends out vibrations parallel to the field and hence
perpendicular to the direction of observation. This gives the central line of the triplet occupying the same
position as the original line and plane polarised with vibrations parallel to the field. The two circular vibrations
which are altered in frequency send out vibrations perpendicular to the field and when viewed sideways appear
as plane polarised vibrations in opposite senses.
Expression for the Zeeman shift: (Using Classical Theory)
Consider an electron in the atom moving in a circular orbit of radius r with a linear velocity v and angular
velocity𝜔. Let e be the charge of the electron and m its mass.
The centripetal force on the electron towards the centre in the absence of the magnetic field is
𝑚𝑣 2
𝐹= = 𝑚𝜔2 𝑟……….. (1)
𝑟
Now let an external magnetic field of flux density B be applied in a
direction perpendicular to the plane of the orbits of the two circular
components and directed towards the reader. Then an additional radial
force of magnitude Bev acts on the electron. The direction of this force
will be outwards from the centre for clockwise motion but inwards
B.Sc. V Semester (P-6) Elements of Atomic, Molecular & Laser Physics A D B F G College, H Halli
towards the centre for anticlockwise motion (Fig). The resulting complex motion of the electron subjected to
an additional radial force is called Larmor precession. This produces a change in the angular velocity without
any change in the form of the orbit. Let δω be the change in angular velocity caused by the field. For the
circular motion in the clockwise direction, the additional radial force is directed away from the centre.
𝐹 − 𝐵𝑒𝑣 = 𝑚(𝜔 + 𝛿𝜔)2 𝑟………. (2)
𝑚𝜔2 𝑟 − 𝐵𝑒𝑣 = 𝑚(𝜔 + 𝛿𝜔)2 𝑟
𝑚𝜔2 𝑟 − 𝑚(𝜔 + 𝛿𝜔)2 𝑟 = 𝐵𝑒𝜔𝑟
𝑚𝜔2 𝑟 − 𝑚𝜔2 𝑟 − 𝑚(𝛿𝜔)2 𝑟 − 2𝑚𝜔. 𝛿𝜔. 𝑟 = 𝐵𝑒𝜔𝑟
−2𝑚𝜔. 𝛿𝜔. 𝑟 = 𝐵𝑒𝜔𝑟 neglecting (𝛿𝜔)2
𝛿𝜔 = −𝐵𝑒/2𝑚 …………. (3)
For the circular motion in the anticlockwise direction, the additional radial force is directed towards the
centre.
𝐹 + 𝐵𝑒𝑣 = 𝑚(𝜔 + 𝛿𝜔)2 𝑟
𝛿𝜔 = 𝐵𝑒/2𝑚
The two cases can be combined into the equation
𝐵𝑒
𝛿𝜔 = ±
2𝑚
If 𝜈 is the frequency of vibration of the electron,
𝛿𝜔
𝜔 = 2𝜋𝜈; 𝛿𝜔 = 2𝜋. 𝛿𝜈 𝑜𝑟 𝛿𝜈 =
2𝜋
Therefore, change in frequency of the spectral line is
𝐵𝑒
𝛿𝜈 = ±
4𝜋𝑚
If 𝜈 𝑎𝑛𝑑 𝜆 are the frequency and wavelength of the original line,
𝑐 −𝑐
𝜈= 𝑜𝑟 𝛿𝜈 = 2 . 𝛿𝜆
𝜆 𝜆
Therefore, the Zeeman Shift,
−𝑐 𝐵𝑒
2
. 𝛿𝜆 = ±
𝜆 4𝜋𝑚
𝑩𝒆𝝀𝟐
𝜹𝝀 = ±
𝟒𝝅𝒎𝒄
𝑗(𝑗+1)+𝑠(𝑠+1)−𝑙(𝑙+1)
• 𝑇ℎ𝑒 𝑞𝑢𝑎𝑛𝑡𝑖𝑡𝑦 1 + = 𝑔, 𝑖𝑠 𝑐𝑎𝑙𝑙𝑒𝑑 𝑡ℎ𝑒 𝐿𝑎𝑛𝑑𝑒 𝑔 𝑓𝑎𝑐𝑡𝑜𝑟.
2𝑗(𝑗+1)

Stark Effect:
The Stark effect is the electrical analogue of the Zeeman effect. The Stark effect is the splitting of spectral
lines due to the action of an external electric field on the radiating substance. Even very strong external electric
fields are weak compared to the interatomic fields. Hence the action of electric field on the motion of the
atomic electrons can be regarded as small perturbations. Consequently, the Stark line splitting is very minute
B.Sc. V Semester (P-6) Elements of Atomic, Molecular & Laser Physics A D B F G College, H Halli
and can be observed only with instruments having a high resolving power. The lines are split into a series of
components (satellites) located, in case of hydrogen, symmetrically on both sides of the original line.
Experimental study:
Here the hydrogen atoms emitting spectral lines are subjected to a powerful electric field. The arrangement
used by Stark is shown in figure.
The canal rays are produced in an ordinary glass discharge
tube provided with a perforated cathode C. When the
pressure in the tube is not very low, discharge takes place
between the anode A and cathode C maintained at a suitable
P.D. The canal rays’ stream through the perforations in the
cathode and form behind the cathode narrow cylindrical
bundles of luminous rays. An auxiliary electrode F is placed
parallel and close to C at a distance of a few millimetres. A
very strong electric field of several thousand volts per metre
is maintained between F and C. The effect produced can be
studied both transversely [Fig (a)] and longitudinally [Fig
(b)]. Stark observed that the lines in the spectrum emitted by the canal rays of hydrogen were split up into
numerous sharp components under the action of the electric field.
Results: The results obtained with the lines of the Balmer series of the hydrogen spectrum are given below:
(i) Every line is split up into a number of sharp components. All hydrogen lines form symmetrical patterns.
The pattern depends markedly on the quantum number n of the term involved. The number of lines and the
total width of the pattern increases with n. Thus, the number of components of 𝐻𝛽 line is greater than that of
the 𝐻𝛼 line; similarly, the number of components of 𝐻𝛾 , is greater than that of 𝐻𝛽 .
(ii) Observation perpendicular to the direction of the electric field (transverse view) shows that the components
are polarised, some parallel to the direction of the field and others perpendicular to it.
(iii) Up to fields of about 107 𝑉/𝑚, the resolution increases in proportion to the field strength
(E). In this region, we have linear or first order Stark effect. When E exceeds 107 𝑉/𝑚, there are shifts in the
line patterns which are proportional to 𝐸2 and we speak of the second-order Stark effect.
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