LESSON SEVEN ELECTRONIC SPECTROSCOPY OF ATOMS

7.1 Introduction

Electronic spectroscopy of atoms deals with the study of the transitions involving electrons in the
valence shell. The electron spin angular momentum and the electronic orbital angular momentum
interact to yield total angular momentum that determines the energy states of the species. The
fine structure of the spectra of species is also dealt with.

7.2 Lesson Learning Outcomes

By the end of this lesson, you will be able to:

i. Understand the electronic structure of atoms
ii. Understand the basis of the electronic spectra of species
iii. Understand the Zeeman Effect

7.2.1 Structure of the Hydrogen-Like Species

+Ze
v

r O -e, m

An electron of charge (-e) and mass (m) revolves round the nuclear charge (+Ze) with velocity 
in a stationary orbit of radius r. (The nucleus has Z protons). For mechanical stability, the
electrostatic force of attraction, f a between the electron and the nucleus must be equal to the
centrifugal force, f c which is operating in the opposite direction. Thus,

fa = − fc (6.02.01)
f a is directly proportional to the product of the charges and inversely proportional to the square
of the distance of separation .

Thus,
(−e)(+ Ze)
fa 
r2
− Ze 2
 fa = (6.02.02)
(4 0 )r 2

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 1
is a proportionality constant in SI units where  0 is the permitivity in vacuum (free space)
4 0
and has the value  0 = 8.854 x10 −12 C 2 N −1m −2 .
mv 2
fc = (6.02.03)
r
Then
fa = − fc
− Ze 2 − mv 2
 =
4 0 r 2 r
Ze 2
 mv 2 = (6.02.04)
4 0 r
From the de Broglie relationship

nh
mvr = (6.02.05)
2
then
nh
v=
2mr
n2h2
 v2 =
4 2 m 2 r 2
(6.02.06)
n2h2
 mv 2 =
4 2 mr 2
Equations (6.02.04) and (6.02.06) yield

Ze 2 n2h2
=
4 0 r 4 2 mr 2
Then
n 2 h 2 0
r= (6.02.07)
mZe2
The radius of the first orbit of the hydrogen atom, when Z = 1 and n = 1 is known as the Bohr
radius. Thus,

12 (6.6262 x10 −34 ) 2 8.854 x10 −12

r1 =
3.142 x9.109 x10 −31 x12 x(1.602 x10 −19 ) 2
= 0.529 x10 −10 m
= 0.0529 angstrom units
(The angstrom unit Å has the value Å = 1x10-10).

Thus, the general form of the radius is given by

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 rn = 0.529n2 Å (6.02.08)

Thus, the radius of a particular orbit in a hydrogen atom is proportional to the square of its principal
quantum number, n.

S.A.Q. 1
Determine the radius, in nm, of the second orbit in the hydrogen atom.

E-tivity -7.2.1 Electronic Spectroscopy of Atoms.

Numbering, pacing and 7.2.1

sequencing
Title Electronic Spectroscopy of Atoms.
Purpose The purpose of this e-tivity is to enable you to describe
Electronic Spectroscopy of Atoms
Brief summary of overall task Read the materials on these links
https://www.youtube.com/watch?v=xe1wl39b44U&ab
_channel=PriyankaJain

https://www.youtube.com/watch?v=2xevoILaxeg&ab_
channel=BUChem

Spark

Individua task a) Describe types of electronic transitions in atomic

spectrocopy

Interaction begins 1. Post two themes that are in atomic electronic

spectra
2. Provide positive and constructive feedback on the
team learners ‘views and ideas. Do this on the
discussion forum 1.2.4

123
 E-moderator interventions 1. Ensure that learners are focused on the contents and
context of discussion.
2. Stimulate further learning and generation of new
ideas.
3. Provide feedback on the learning progress.
4. Round-up the e-tivity
Schedule and time This task should take two hours
Next Energy of an Electron in a Hydrogen-Like Species

7.2.2 Energy of an Electron in a Hydrogen-Like Species

The total energy, En, of an electron in an orbit of he hydrogen-like species is a sum of the potential
energy, p.e, and the kinetic energy, k.e. Thus, with n being the principal quantum number,

En = p.e + k.e (6.03.01)

The potential energy of the electron is ‘the work necessary to take the electron to infinity from its
equilibrium position r, with respect to the nucleus.’ Since the Coulombic force, f a , between the
electron and the nucleus is given by :

− Ze 2
fa = (6.03.02)
4 0 r 2
the potential energy is given by :

p.e. = f r
a dr

− Ze 2

= dr (6.03.03)
r 4 0 r
2

− Ze 2
=
4 0 r
The negative sign indicates that work must be done on the electron to remove it. Kinetic energy is
given by:

mv 2
k.e. = .
2
Then,
mv 2 Ze 2
En = − (6.03.04)
2 4 0 r
But,

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 Ze 2
mv 2 =
4 0 r
(6.03.05)
mv 2 Ze 2
 =
2 8 0 r
Thus, substitution of (6.03.05) into (6.03.04) yields:
Ze 2 Ze 2
En = −
8 0 r 4 0 r
(6.03.06)
− Ze 2
=
8 0 r
Substitution for r from equation (6.02.07) into equation (6.03.06) yields;
− me 4 Z 2
En = 2 2 2 (6.03.07)
n h 8 0
The negative sign denotes the fact that there is attraction between the nucleus and the electron and
so work must be done to remove it to a distance greater than the equilibrium distance, r, from the
nucleus. Substitution for the various constants into equation (6.03.07) yields
− 2.122 x10 −18
En = J (6.03.08)
n2
Z = 1 for hydrogen. In the first orbit n = 1 and the energy of the electron is :

E1 = -2.122x10-18 J.

S.A.Q 2
Determine the energy, in kJ mol-1, of the third orbit in the hydrogen atom.

7.2.3 Electronic Spectra of the Hydrogen-Like Species

The theory developed in the earlier sections of the current unit is useful in calculating the
frequencies of the spectral lines in the atomic spectra of the hydrogen atom (and the hydrogen-like
species). Let E1 and E2 represent the energies at the inner and outer quantum number values n1 and
n2 respectively.

Then,
− Z 2e4m 1
E1 = x 2 (6.04.01)
8 02 h 2 n1
− Z 2e4m 1
E2 = x 2 (6.04.02)
8 02 h 2 n2
The amount of energy emitted when an electron jumps from an outer level n2 to an inner level n1
is given by:

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 − Ze 4 m 1 − Z 2e4m 1
E 2 − E1 = x − x 2
8 02 h 2 n22 8 02 h 2 n1
(6.04.03)
Z 2e4 m  1 1 
=  − 2 
2 2  2
8 0 h  n1 n2 
The quantity represented by equation (6.04.03) is denoted E and is given out as a photon of
electromagnetic radiation.
Since
c
 = c  = (6.04.04)

then,
E = h
hc (6.04.05)
=

Equations (6.04.03) and (6.04.05) then yield:
hc Z 2e4m  1 1 
= 2 2  2
 − 2 
 8 0 h  n1 n2 
(6.04.06)
1 Z 2e4m  1 1 
 =  − 
 8 02 h 3 c  n12 n22 

1
The term is the wave number, and is given the symbol  . Hence,

Z 2e4m  1 1 
 = 2 3  2 − 2  (6.04.07)
8 0 h c  n1 n 2 
Z 2e4m
The term is called the Rydberg constant. For the hydrogen atom this is denoted by RH.
8 02 h 3 c
Thus,
12 (1.602 x10 −19 ) 4 (9.109 x10 −31 )
RH =
8 x(8.854 x10 −12 ) 2 x(6.6262 x10 −34 ) 3 x(2.997 x10 8 ) (6.04.08)
= 1.097 x10 7 m −1
For the hydrogen atom then,

 1 1 
 = RH  2 − 2  (6.04.09)
 n1 n2 
From equation (6.04.07), the wave number for the hydrogen-like species is given by
 1 1 
 = RH Z 2  2 − 2 
 n1 n2 
where Z is the atomic number of the species .

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Equation (6.04.09) explains the following spectral transitions:

NAME n1 n2 REGION
Lyman 1 2, 3, 4, … UV
Balmer 2 3, 4, 5, … Visible
Paschen 3 4, 5, 6, …. IR
Brackett 4 5, 6, 7, … IR
Pfund 5 6, 7, 8, … IR

The above chart may be depicted diagrammatically, as shown below.

S.A.Q 3
Determine the frequency of the radiation emitted when an electron in a hydrogen atom jumps from
the orbit with n = 3 to the orbit with n = 2.

Note:
In the fore-going derivations, it is taken that the electron moves in a circular orbits around the
nucleus. This is not strictly the case. The accurate situation is obtained through solution of the
Schrödinger equation for a single electron moving a nucleus. The solutions yield quantum
numbers: n, l, and m which are related as follows:

(1) The principal quantum number n, determines the energy of the electron. It takes
integral values 1, 2, …, ∞.

(2) The angular momentum quantum number, l, takes integral values depending on n
as follows: l = 0, 1, 2, … , (n-1). l determines the shape of the orbital and the
following notation is pertinent.
]
l 0 1 2 3 ….
Notation s p d F
l also determines the angular momentum of the electron in the orbital

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 (3) The magnetic quantum number, m, takes integral values depending on l as follows:
m = l, ( l-1), …0, …-l. m determines the orientation of the orbital in space.

In an orbital, the electron has a spin quantum number, s = ½. Thus, four quantum numbers, n, l,
m, and s are used to express the state of an electron in an atom.

7.2.4 The Hydrogen Atom Spectrum

However large an atom is, its electrons take up orbitals of the s, p, d, f … type and so the overall
shape of each electron’s domain is unaltered. The energy of each orbital, on the other hand, varies
considerably from atom to atom. The two main factors which contribute to the determination of
this energy are:

(a) attraction between electrons and nucleus , in the same atom and
(b) repulsion between electrons of the same atom .

The case of the hydrogen atom is the simplest since no inter-electron repulsion occurs. This leads
to all orbitals having the same value of the principal quantum number, n, being degenerate. Earlier
considerations show that:

me 4
En = − 2 2 2 J , (n = 1 , 2 , ... ) (6.05.01)
8h  0 n
In reciprocal units,

me 4 RH
n = − = − , (n = 1 , 2 , ... ) (6.05.02)
8h 3 c 02 n 2 n2
RH = Rydberg constant for hydrogen = 109,677.581 cm-1 = 1.097x107 m-1
o = permitivity of free space= 8.854 x 10-12 C2 N-1 m2.

The lowest value of n, when n = 1, is :

1 = - RH cm-1.
∞ = 0 implies complete removal of the electron from the atom.

The ‘selection rules’ for transitions in the hydrogen atom are:

(i) n = anything,  no limitation
(ii) l = 1 only

One sees immediately that an electron in the 1s ground state can undergo a transition to any p state.
Thus, 1s→ np, n  2, while a 2p electron can undergo transition to either an s or a d state: 2p →
ns or nd. These are sketched below:

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 n=5 5s 5p 5d
n=4 4s 4p 4d

n=3 3s 3p 3d

n=2 2s 2p

n=1 1s
This completes the study of the coarse structure of the hydrogen spectrum. To understand the fine
structure, one needs to know how other quantum numbers affect the electronic energy levels. This
will come out clearly in the next few sections.

7.2.5 Orbital Angular Momentum

An electron moving in its orbital possesses orbital angular momentum represented by the orbital
angular momentum quantum number I and given as:
h
I = l (l + 1) . (6.06.01)
2
where l is the orbital angular momentum quantum number

Orbital angular momentum is a vector quantity, and hence has both magnitude and direction. This
vector can point only so that its projections, lz, along a reference direction are integral multiples of
h
. For l = 1, lz = +1, 0, -1. This is represented thus:
2

It is to be noted that the dependence of lz on l is as depicted below:

l z = l , l − 1 , . . . , 0 , . . . , − (l − 1) , − l

7.2.6 Electron Spin Angular Momentum

The electron spin is associated with the quantum number ½. Thus, spin angular momentum, S, is
given by:

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 h
S = s ( s + 1) .
2

h
For a single electron, then, S = ½ 3 .
2

The quantization law for spin momentum is that the vector S can point only so that it has
h
components in the reference direction which are half-integral multiples of .
2

For S = ½, sz = +½, –½. It is to be noted that there will be 2S+1 states.

7.2.7 Total Electronic Angular Momentum

The total electronic angular momentum is a combination of both orbital angular momentum and
spin angular momentum and is a vector quantity. This is represented by the symbol j, (for a single
electron), and J, for many electrons. Formally, j = l + s,

where
l = orbital angular momentum,
s = spin angular momentum.

This is vector addition. j may also be represented in terms of the total angular momentum quantum
number j. Then,
h
j = j ( j + 1) (6.08.01)
2

j has components in a reference direction, denoted by jz, and determined by:

jz = j, (j-1), (j-2), ..., ½.

Deduction of j for particular values of l and s

If the components along a common direction of two vectors are added, the summations yield the
components in that direction of their resultant. For a single electron system with l = 1, the lz
components are lz = -1, 0, +1. Similarly for s = ½, one has sz = -½, ½. Taking all possible sums of
the above quantities yields

j z = l z + sz

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 = -3/2, -½, -½, ½, ½, 3/2

The maximum value is 3/2 which belongs to jz = 3/2. Other components of jz = 3/2 are ½, -½ and
-3/2. Striking these from the list leaves jz = -½, ½ which are consistent with j = ½. Thus all the six
components are accounted for j = 3/2 and j = ½. Hence, for a p orbital (i.e. l = 1) the orbital and
spin momenta may be combined to produce a total momentum of

3 5 h 1 h
j= ( ) = 15 , when l and s reinforce one another and
2 2 2π 2 2π

1 3 h 1 h
j= ( ) = 3 , when l and s oppose one another.
2 2 2π 2 2π

These two values of j represent two different energy states. The energy states are represented by
2s+1
LJ. In terminology analogous with that for atomic orbitals, then one has:

L 0 1 2 3
Symbol S P D F

For the two states noted above, 2S+1 = 2x½ + 1 = 2, and the states are referred to as doublets.
Hence, one has 2P3/2, 2P½. These notations represent what are referred to as states or terms.

7.2.8 The Fine Structure of the Hydrogen Atom Spectrum

The hydrogen atom contains only one electron and so the coupling of the orbital and spin momenta
produces the following terms: For the p-orbital occupancy:

L=1
2
S = ½; 2S+1 = 2 P3/2, ½
J = 3/2, ½
For the d-orbital occupancy:
L=2
2
S = ½; 2S+1 = 2 D5/2, 3/2
J = 5/2, 3/2
For the s-orbital occupancy:

L=0
2
S = ½; 2S+1 = 2 S½
J=½
The selection rules are:

Δn = anything,
ΔS = 0, ΔL = ±1, ΔJ = 0, ±1.
These selection rules indicate that transitions are allowed between any S level and any P level.
Thus, the spectrum to be expected from the ground (1s) state will be identical with the Lyman
series except that ‘every line is a doublet’.

131
This situation is represented thus:

S.A.Q. 4
Determine whether the following electronic transitions in the hydrogen atom are allowed or not:
2
S½ → 2P3/2
2
P½ → 2D5/2
2
P½ → 2S ½

7.2.9 The Many-Electron Atoms and the Russell-Saunders Coupling

When a set of orbitals of given n and l is filled, it is referred to as a closed shell e.g. 1s2, 2s2, 2p6,
3d10 etc. The convenience of this is that closed shells make no contribution to the orbital or spin
angular momentum of the whole atom and hence may be ignored when discussing atomic spectra.
The alkali metals, lithium, sodium, potassium, rubidium and cesium have a single electron outside
a closed-shell core. These then resemble hydrogen and the angular momentum of the core is
ignored and one deals with the spin and orbital angular momentum of the outer electron. The p, d
etc levels are split into doublets. The ‘selection rules’ for alkali metals are the same as those for
hydrogen.
2S+1
LJ
ΔS = 0; ΔL = 1; J = 0,  1.

132
The energy levels and transitions for lithium are sketched below:

The L-S coupling scheme for two electrons is summarized as follows:

L = l1+l2, l1+l2-1, l1+l2-2… , l1 - l2 

S =  si, si – 1, … , ½ or 0.

J = L + S, …, L - S

The selection rules are:

S = 0; L = 1; S = 0; 1.

What follows is an illustration of the many-electron case through consideration of the spectrum of
helium and the alkaline earths.

The ground state for helium has the configuration 1s2. This yields:

133
 L = l1 + l2 = 0 + 0 = 0
S = ½ + (-½) = 0
2S + 1 = 0 + 1 = 1
J=0
Hence the ground state is the singlet 1S0 state. The selection rules are the same as those for many-
electron atoms.

Consideration One
Suppose that in the case of the helium atom, only one electron undergoes transitions leaving the
other in the 1s orbital, and that the spins are opposite. The transitions will be to other singlet states,
as shown below:

Consideration Two

This is the case when electron spins are parallel. The lowest configuration is 1s2s. Then, S = 1, 2S
+ 1 = 3; L = 0, and J = 1. The state is 3S1. The transitions will be to 1snp configuration whose:

L = 1; S = 1, 2S + 1 = 3; J = 2, 1, 0; and the states are 3P2, 1, 0

134
7.2.10 Summary
This unit has dealt with transitions of electrons amongst the energy levels of atoms. The electronic
energies, like all types of energy, are quantized. Movement of electronic charge, in atoms, causes
interaction with the electric component of electromagnetic radiation leading to atomic spectra. The
energy levels in atoms and molecules are referred to as Terms. Transitions between Terms are
governed by ‘Selection rules’ that are derived, for a system, from quantum mechanics.

7.11 Terminal Questions

Q.1. Determine the wave numbers, in m-1, of the first three lines in the absorption spectrum arising
from transitions from the 3s level of the hydrogen atom. What is the ionization energy, in kJmole-
1
, of this level?

Q.2. What are the term symbols for the following pairs of equivalent electrons?
(a) p2
(b) d2

Q.3.Explain whether the following transitions are allowed or not:

(a) 2
S0 → 2
P1
(b) 3
P1 → 4
D2

S.AQ. 1
Use of equation (6.02.08) yields r2 = 0.529x22x10-10 m
= 0.529x4x10-1x10-9
= 0.2116x10-9 m
= 0.2116 nm
S.A.Q.2
Use of equation (6.03.08) yields:

− 2.122 x10 −18

E3 ( N A ) = x6.022 x10 23
32
= −141985 .38 J
= −141 .98538 kJmole −1 .
S.A.Q. 3
For the hydrogen atom:
 1 1 
 = 1.097 x10 7  2
− 2  m −1 , n1  n2 .
 n1 n2 
With n1 = 2 and n2 = 3, then -1 = 1523611.1 m-1
 = c-1
= 4.553 x 1014 Hz
S.A.Q. 4
The selection rules, equation (6.09.04), allow the following conclusions to be made:

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 Transition Conclusion
2
S½ → 2P3/2 allowed
2
P½ → 2D5/2 not allowed, J = 2  1
2
P½ → 2S ½ allowed

6.13 Answers to S.A.Qs

S.AQ. 1
Use of equation (6.02.08) yields r2 = 0.529x22x10-10 m
= 0.529x4x10-1x10-9
= 0.2116x10-9 m
= 0.2116 nm
S.A.Q.2
Use of equation (6.03.08) yields:

− 2.122 x10 −18

E3 ( N A ) = 2
x6.022 x10 23
3
= −141985 .38 J
= −141 .98538 kJmole −1 .
S.A.Q. 3
For the hydrogen atom:
 1 1  −1
 = 1.097 x10 7  2
− m
2 
, n1  n2 .
 1
n n 2 

With n1 = 2 and n2 = 3, then -1 = 1523611.1 m-1

 = c-1= 4.553 x 1014 Hz
S.A.Q. 4
The selection rules, equation (6.09.04), allow the following conclusions to be made:

Transition Conclusion

2
S½ → 2P3/2 allowed
2
P½ → 2D5/2 not allowed, J = 2  1
2
P½ → 2S ½ allowed

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