UNIT-1

3. Electromagnetic radiations are emitted if an electron jumps from stationary

INTRODUCTION TO ATOMIC STRUCTURE AND SPECTROSCOPY orbit of energy E2 to another stationary orbit of lower energy El. frequency
υ of the emitted radiation is related by the equation
❖ BOHR'S ATOMIC MODEL: (postulates of Bohr model)
E2-E1= h υ --------------- (3)
Bohr developed his theory of atomic structure by retaining the two Now we shall calculate some quantities
essential features of Rutherford's planetary model, i.e. (a) Radii of orbits:
From equation (2), we have
1. The atom consists of a central positively charged hard core called the
nucleus, and the electrons travelling round the nucleus in circular orbits Substituting this value of in equation (1)
𝑣 = 𝑛ℎ / 2 π 𝑚 𝑟

2. The outward centrifugal force is balanced by the net electrostatic attraction

towards the nucleus.
3. He assumed that an electron in the field of nucleus having the orbital =
𝑒2 𝑚 nh 2

angular momentum is equal to an integral multiple of h/2π.

4 π ε0 𝑟 2 𝑟
(2 π 𝑚 𝑟)

4. The angular momentum of electron around nucleus is mvr, hence

mvr = n h/2π r=
𝑚𝑛2 ℎ2 4πε0 𝑟 2
=
𝑛 2 ℎ 2 ε0

where n = 1,2,3 for first, second and third orbit respectively and h is Planck's in general
4π2 𝑚2 𝑟 2 𝑒 2 π m𝑒 2

constant. Such orbits are known as stationary orbits.

rn = --------------(4)
5. The radiation of energy takes place only when an electron jumps from orbit
𝑛 2 ℎ 2 ε0

of higher energy to another orbit of lower energy.

π m𝑒 2

b) velocity of revolving electrons:

The difference of energies is equal to hυ, i.e., To obtain velocity of revolving electron, we substitute the value of r
E2-E1= hυ from equation (4) in eq (2)

❖ BOHR'S THEORY OF HYDROGEN ATOM:

𝑛 2 ℎ 2 ε0 𝑛ℎ
π m𝑒 2
mv ( )= 2π

Bohr's theory of hydrogen atom is based on the following assumptions v= ---------(5)

𝑛ℎ π m𝑒 2 1 𝑒2

1. An electron in an atom moves in a circular orbit about the nucleus under

2π 𝑛2 ℎ2 ε0 𝑚 2𝑛ℎε0
=

the influence of Coulomb's force of attraction between the electron and c) Orbital frequency of electron:
nucleus. As the atom as a whole is stable, the Coulombian force of The orbital frequency of electron is given by
attraction is balanced by Newtonian centrifugal force (fig.), i.e.,

υ=
= -------------------(1)
1
𝑒2 𝑚𝑣 2
𝑇

=
4 π ε0 𝑟 2 2
𝑣

2. Only those orbits are possible for which the orbital angular momentum of
2πr

the electron is equal to an integral multiple of h/2π i.e., =

𝑒2 1 π m 𝑒2
----------------(6a)
2𝑛ℎε0 2 π n2 ℎ2 ε0

mvr = ------------------------(2) The time period of revolution is given by

𝑛ℎ

T= -----------------------(6b)
2𝜋
4ε0 2 n3 ℎ3
𝑚𝑒 4
d) Electron energy:
𝑚𝑒 4 𝟏 𝟏

The electron energy consists of two types

8 ℎ 3 ε0 2 1 𝑛2 2
𝛖 =( )[𝑛 2 − ]

1) Kinetic energy: kinetic energy is due to the motion of the If cis the velocity of light and λ is the wavelength, then υ = c / λ
electron and its value is 𝑐 𝑚𝑒 4 𝟏 𝟏

where v is the velocity of electron

λ 8 ℎ 3 ε0 2 1 𝑛2 2
=( )[𝑛 2 − ]
1
2

K.E =
𝑚𝑣 2
1 𝑚𝑒 4 𝟏 𝟏
2
1 1 𝑒2 λ 8𝑐 ℎ 3 ε0 2 1 𝑛2 2
=( )[𝑛 2 − ]
2 2 2𝑛ℎε0

K.E =
𝑚𝑣 2 = 𝑚 [ ]
𝑚𝑒 4 1 𝟏 𝟏
8𝑛2 ℎ2 ε0 2 λ 𝑛1 2 𝑛2 2
= 𝑹[ − ]

2) Potential energy: The potential energy is due to the fact that electron
𝑚𝑒 4

lies in the electric field of positive nucleus. We know that potential is 10.97 x 106 m-1
8𝑐 ℎ 3 ε0 2
𝑹=( ) it is called Rydberg’s constant and its value

at a distance r from the nucleus is

ῡ is called wave number.
1 𝟏 𝟏
λ 𝑛1 2 𝑛2 2

V=
ῡ = = 𝑹[ − ]
𝑒

❖ QUANTUM NUMBERS ASSOCIATED WITH VECTOR ATOM MODEL:

4πε0 𝑟

Thus the potential energy of electron of charge (-e) is

The quantum numbers associated with each of the electrons in a given
P.E. = V (-e) = atom are the following:
−𝑒 2

1. The principal or total quantum number (n).

4πε0 𝑟

= = 2. Orbital quantum number (ℓ).

−𝑒 2 π m 𝑒 2 −𝑚𝑒 4

3. Spin quantum number (s).

4πε0 𝑛2 ℎ2 ε0 4𝑛2 ℎ2 ε0 2

So total energy is 4. Total angular quantum number (j).

En = K.E + P.E 5. Magnetic orbital quantum number (ml).
6. Magnetic spin quantum number (ms ).
= + 7. Magnetic total angular momentum quantum number (mj).
𝑚𝑒 4 −𝑚𝑒 4
8𝑛2 ℎ 2 ε0 2 4𝑛2 ℎ2 ε0 2

En =
−𝑚𝑒 4
The principal or Total Quantum Number (n)
8𝑛2 ℎ2 ε0 2
1. This quantum number belongs to the principal orbit to which the electron
belongs.
2. It indicates major energy states of electron around the nucleus.
3. The total quantum number n can have only non-zero positive integral
values, i.e., n =1,2,3, . . .
(e) Frequency of emitted radiation: The frequency of emitted radiation
The energy levels or shells of electrons corresponding to n = 1, 2, 3, 4, 5,
can be found from the following relation
6, 7 are denoted by letters K, L, M, N, O, P, Q respectively.
𝐡 𝛖 = 𝐸𝑛2 − 𝐸𝑛1 The number of electrons in a shell is limited to 2n2
−𝑚𝑒 4 −𝑚𝑒 4
2
8 𝑛2 2 ℎ 2 ε0 2 1 ℎ 2 ε0 2
𝐡𝛖 =( ) - (8 𝑛 )

𝑚𝑒 4 𝟏 𝟏
8 ℎ 2 ε0 2 1 𝑛2 2
𝐡𝛖 =( )[𝑛 2 − ]
 Orbital Quantum Number ℓ : Magnetic Spin Quantum Number ms :
1. The projection of spin vector s (representing spin angular
1. This quantum number defines the shape of the orbital occupied by
momentum of electron) in the magnetic field direction is called
the electron and the orbital angular momentum of the electron.
magnetic spin quantum number ms.
2. Due to this fact this quantum number is also referred to as orbital or
2. It tells about the splitting of s in the presence of magnetic field.
angular quantum number.
3. The possible values of ℓ is 0 to (n — 1).
4. The orbitals corresponding to ℓ = 0, l, 2, 3 etc. are designated as s, p, total 2s+1 values.
The value of ms = s 𝐜𝐨𝐬 𝜽 and the possible values are from -s to +s

d, f, etc. respectively.
Spin Quantum Number (s) : Magnetic Total Angular Momentum Quantum Number mJ:

1. This quantum number has been introduced to account for the spin of the 1. The projection of the total angular momentum vector j on the field
electrons about their own axis. direction is called Magnetic Total Angular Momentum Quantum
Number mj.
2. The magnitude is always half. Since the electron can spin clockwise or 2. It tells about the splitting of j in the presence of magnetic field. The
anticlockwise, there are two values given to s are (+1/2 and -1/2) possible values of mj are
depending upon whether the electron spins in one direction or the other. - j to +j and total 2j+1 values.

Total Angular Quantum Number j: ❖ Coupling schemes

1. L-S Coupling
1. This quantum number represents the resultant angular momentum of 2. j-j coupling
the electron due to both orbital and spin motions, Its numerical value is L-S Coupling:
vector sum of ℓ and s. This type of coupling occurs most frequently and hence is known as
normal coupling.
2. It is usually expressed as j = (ℓ ± s), plus sign is used when s is
parallel to ℓ and minus when s is antiparallel to ℓ

Magnetic Orbital Quantum Number mℓ:

1. When an atom is placed in a strong magnetic field, the electrons with

same values of principal quantum number (n) and orbital quantum
number (ℓ), may still differ in their behaviour.
2. To explain this behaviuor we require one more quantum number m ℓ,
known as magnetic orbital quantum number has been introduced.
3. It tells about the splitting of ℓ in the presence of magnetic field.
4. It is defined as “The projection of ℓ in the magnetic field direction is
called magnetic orbital quantum number m ℓ.

The possible values of m ℓ is from - ℓ to + ℓ and total 2 ℓ +1 values

In this coupling all the orbital angular momentum vectors ℓ of the
its value is m ℓ = ℓcos 𝜃

electrons combine to form a resultant vector L and all the spin angular
momentum vectors s combines to form a resultant vector S and vectors
L and S combine to form a vector J which represents total angular
momentum of the atom.
 L = (ℓ 1+ ℓ 2+ ℓ 3+……)
To express the spectral terms, we consider the following two points:
S = (s1+s2+s3+…...)
J=L+S
1. The value of total angular momentum of the atom (J) is written as the
j-j coupling : subscript at the lower right of the letter representing the particular L value
In j-j coupling, each electron is considered separately and its total angular of the atomic state.
momentum j is obtained by the 2. The number of possible values of J for given values of L is written as a
relation subscript at the upper left hand of the letter representing the L values.
j=ℓ+s
Then the total angular momentum J of the atom would be vector sum of Example: For L = 1 and S =1/2 the spectral terms are
all the individual j vectors of the
electrons. Thus, j1 = (ℓ 1 + s1), j2 = (ℓ 2 + s2), j3 = (ℓ 3 + s3), …….
And J = j1+j2+j3+……….
2𝑃3/2 and 2𝑃1/2

❖ SELECTION RULES

We know that in an atom, there are a number of energy states. It is observed

that all the transitions
between different energy states (as spectral lines) do not appear. Only
some spectral lines are possible.
The spectral lines are governed under certain principles known as selection
rules.

There are four selection rules as described below:

1. The selection rule for L: Only those lines are observed for which the
value of L changes by ± 1 (i.e., ∆L = ± 1).
❖ SPECTRAL TERMS AND SPECTRAL NOTATION 2. The selection rule for J: Only those spectral lines are observed when the
transitions take place between states for which ∆J = ± 1 or 0. The transition
0 to 0 is not allowed.
In describing the electron configuration, small letters are used to represent
3. The selection rule for S: Only those spectral lines are observed for which
the ℓ values. Thus, if an electron is
the value of S changes by 0 (i.e., ∆S = 0).
in a shell for ℓ = 0, it is called s-electron, for ℓ = 1, 4. Selection rules for magnetic quantum numbers: In the presence of
p-electron and so on. magnetic field, the orbital magnetic quantum number m ℓ and spin magnetic
quantum number ms play an important part in the transition. Their selection
To represent the configuration, following two points are considered: rules are
∆m ℓ = 0 or ± 1 and ∆ms = 0.
1. The value of total quantum number n is written as a prefix to the letter In consequence ∆mJ = 0 or ±1.
representing its ℓ value.
2. The number of electrons written at the upper right-hand side of letter
representing their ℓ value.
Example: Sodium (11 electrons) 1s2 2 s2 2 p6 3sl
 ❖ STERN-GERLACH EXPERIMENT 7. The splitting of silver beam into two components in inhomogeneous field
(Verification of Spatial quantization and Spin of electron) verifies the existence of electron spin and the postulate of space quantization.
Expression for displacement of atom along field direction:
Experimental Arrangement: Suppose the magnetic field be non-homogeneous along Y-direction. The
1. In Stern and Gerlach experiment a beam of silver atom is passed Field gradient is and is positive.
through an inhomogeneous magnetic field.
𝒅𝑩

2. The silver atom beam is produced by heating silver in a small electric

Let the atomic magnet with magnetic moment M, pole strength p and length
𝒅𝒚

oven O and then passing the beam through slits Sl and S2 (collimator) ℓ inclined at an angle θ with the field direction. If the field strength at one pole
is B, then the field strength at another pole will be

(B + ) ℓ cos θ.
𝒅𝑩
𝒅𝒚

Force on one pole of atomic magnet is p B while on other pole is p

(B + ) ℓ cos θ. The extra force p ℓ cos θ on one pole displaces
𝒅𝑩 𝒅𝑩

the atom as a whole.

𝒅𝒚 𝒅𝒚

The force Fy is given by

Fy = p ℓ cos θ
𝒅𝑩

Fy = M cos θ -----------(1)
𝒅𝒚
𝒅𝑩

where p ℓ = M is called magnetic moment

𝒅𝒚

Due to this force, the atomic magnet will be displaced from its straight
3. The inhomogeneous magnetic field is produced having one of the pole path in the field direction.
pieces of the magnet flat with a cylindrical groove and the other in the To find out this displacement, let the silver atom enter the non-
form of a knife edge, parallel to the groove as shown in the figure. homogeneous field with velocity v and
4. Thus, the magnetic field is of much greater intensity near the knife edge the length of path be L for which time taken is t.
than anywhere else in the gap, i.e., the intensity of the magnetic field
The displacement (d)y of the atom along the field direction at the end of time t is given
increases as we go from the center towards the knife edge pole and by
decreases as we go towards the other pole.
5. A photographic plate P(detector) records the configuration of the beam (d)y = ay t2 -----------------------------(2)
𝟏

after its passage through the field.

where ay is the acceleration imparted to the atom along the field
𝟐

6. In the absence of magnetic field, a trace of the form of a narrow strip is direction by force Fy .
obtained as shown in fig. In the presence of the inhomogeneous thus, ay =
𝐹𝑦
where m is the mass of the particle.
magnetic field the strip splits up into two components as shown in fig. 𝒎

1 𝐹𝑦 1 𝐹𝑦 𝐿 2 𝐿
2 𝑚 2 𝑚
𝑑𝑦 = ( ) 𝑡 2 = (𝑣) (𝑡 = 𝑣)

Substituting value of Fy from eq. (1), we get

-------------------------(3)
1 𝑀cos θ 𝑑𝐵 𝐿 2
2 𝑚 𝑑𝑦
𝑑𝑦 = (𝑣)
 ❖ ZEEMAN EFFECT
In 1896, Prof. Zeeman discovered that when a source of radiation, giving
line spectrum is placed in a magnetic field, the spectral lines are split up
into a number of component lines, symmetrically distributed about the
original line. Doublets, triplets and even more complex systems are
observed. This is known as Zeeman effect.
A. If the magnetic field is very strong, each spectral line is split up into
two components in the longitudinal view and in three components
in transverse view. This is known as Normal Zeeman effect.
B. When the magnetic field is comparatively weak, each line splits into
more than three lines. This is known as Anomalous Zeeman Effect.

Experimental Arrangement
The experimental arrangement for observing normal Zeeman effect is shown in fig

1. Source of radiation such as sodium flame or a mercury arc (L) is placed

between the pole pieces of a powerful electromagnet.
2. The electromagnet has conical polepieces and holes are drilled along the
length so that light from the source can pass through it.
3. Thus, the spectrum can be observed along the direction of magnetic field. The
spectral lines are observed with a high resolving power spectroscope.
4. The spectral lines may also be observed in a direction perpendicular to the
magnetic field.
5. Perpendicular to the direction of magnetic field (normal transverse Zeeman
Effect) three components are observed.one in the same position as the
original frequency ν and two components being on either side of the central
line and equally separated from it having frequencies ν + ∆ν and ν - ∆ν
6. When the light is viewed along the direction of magnetic field, (normal
longitudinal Zeeman
effect), the same two additional lines with frequencies ν + ∆ν and ν - ∆ν are
observed while the central line having frequency ν is missing.
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