Quantum Chemistry

Introduction
 Concerned with the interaction of matter with electromagnetic radiation
 Spectroscopic measurements combined with theoretical interpretations provide detailed
information about chemical structure and the arrangement of electrons in atoms and molecules;
also useful in quantification of substances.

𝐸𝐸𝐸𝐸𝐸𝐸𝐸𝐸𝐸𝐸𝐸𝐸𝐸𝐸𝐸𝐸𝐸𝐸𝐸𝐸𝐸𝐸𝐸𝐸𝐸𝐸𝐸𝐸𝐸𝐸 𝑆𝑆𝑆𝑆𝑆𝑆𝑆𝑆𝑆𝑆𝑆𝑆𝑆𝑆𝑆𝑆
(𝑆𝑆𝑆𝑆𝑆𝑆 ℎ𝑎𝑎𝑎𝑎𝑎𝑎𝑎𝑎𝑎𝑎𝑎𝑎)

Visible light and other different types of radiation – in vacuum all travel with same speed, viz
2,998 x 108 m s−1

 Electromagnetic radiation by a wavelength λ and frequency ν, related by

λν = c C ≡speed of light

S.I unit for λ is metre (m)

S.I unit for ν is (s−1) second−1 or Hertz (Hz)

Note: {1 Å = 10−10 m, 1 nm = 10−9 nm}

An electromagnetic wave is different from other types of waves (eg sound waves, water waves,
seismic waves, and waves caused by musical instruments) – essential difference is it can travel
through a vacuum - ⸫ medium is not essential.

 However, when electromagnetic wave comes in contact with matter – we have important
interactions that affect the wave and the material.

Period τ

𝟏𝟏
Frequency ν = 𝛕𝛕

𝟏𝟏 𝒌𝒌
using Hooke’s law : ν = 𝟐𝟐𝟐𝟐 � 𝒎𝒎𝒏𝒏 here 𝒌𝒌𝒏𝒏 = Force constant

Wavenumber (ν¯) 𝟏𝟏 unit: m−1

(ν¯) =
λ

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Emission and Absorption spectra
Spectra can result from either emission of absorption of energy.
Emission Spectrum
1. In order to observe an emission spectrum, the substance must be excited in some way.
2. This may be done for an atomic species – by introducing it into a flame or by passing
an electric discharge through it.
3. If emitted light is observed through a spectrometer – the characteristic emission
spectrum of substance will be seen.

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Absorption Spectrum

1. The absorption spectrum can be observed by passing continuous radiations, such as

white light, through a substance in the vapour phase or in solution and observing the
spectrum with a spectrometer.
2. When this is done, certain wavelengths are missing from the spectrum for eg. if
continuous radiation of white is used its normal spectrum consists of colours from red
to violet which blend smoothly into one other.
3. After the white light has passed through the substances, the absorption spectrum now
consists of black lines superimposed on the continuous spectrum.
4. These black lines occur because the substances through which the light passed has
removed (absorbed) light corresponding to certain wavelengths.
5. The energy of a transition causing such a line is given by

hν = E2 − E1

where ν = frequency of spectral line, E2, E1 = states of energy 2 and 1 respectively,

h ≡ Plancks constant

6. It is possible to calculate energy associated with absorption in a specific region of

spectrum. Energy per mole ϵ

E = Lϵ

= Lhν

𝟔𝟔,𝟎𝟎𝟎𝟎𝟎𝟎 × 𝟏𝟏𝟏𝟏𝟐𝟐𝟐𝟐 �𝒎𝒎𝒎𝒎𝒎𝒎−𝟏𝟏 � ×𝟔𝟔,𝟔𝟔𝟔𝟔𝟔𝟔 × 𝟏𝟏𝟏𝟏−𝟑𝟑𝟑𝟑 (𝑱𝑱𝑱𝑱)×𝟐𝟐,𝟗𝟗𝟗𝟗𝟖𝟖 × 𝟏𝟏𝟏𝟏𝟖𝟖 �𝒎𝒎𝒔𝒔−𝟏𝟏 � ×𝟏𝟏𝟏𝟏−𝟑𝟑 (𝒌𝒌𝒌𝒌/𝒎𝒎𝒎𝒎𝒎𝒎)
= 𝟏𝟏𝟏𝟏−𝟗𝟗 (𝒎𝒎 𝒏𝒏𝒏𝒏−𝟏𝟏 )×λ

𝟏𝟏,𝟏𝟏𝟏𝟏𝟏𝟏 ×𝟏𝟏𝟏𝟏−𝟓𝟓
E= 𝒌𝒌𝒌𝒌 𝒎𝒎𝒎𝒎𝒎𝒎−𝟏𝟏
λ/𝒏𝒏𝒏𝒏

eg. Calculate the energy is kJ mol-1 corresponding to absorption at 400 nm

𝟏𝟏,𝟏𝟏𝟏𝟏𝟏𝟏 ×𝟏𝟏𝟏𝟏−𝟓𝟓
Solution: E = 𝟒𝟒𝟒𝟒𝟎𝟎

= 2,99 × 102 kJ/mol

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Application of Emission and Absorption Theory:
1. Lambert’s Law
 these laws are concerned with the intensities of light absorbed or transmitted when incident
light is passed through some material

The reduction is intensity dI that occurs when light passes through a layer of thickness dl is
given by

dI = −bI dl (1) // b = constant

2. Beer’s Law
Beer studied the influence of concentration of a substance in solution on absorbance – and
found same line relationship between concentration and absorbance (as found Lambert found
between absorbance and thickness

Beers Law States that

𝐼𝐼𝑜𝑜
log = 𝐴𝐴 = 𝐶𝐶𝐶𝐶𝐶𝐶𝐶𝐶𝐶𝐶𝐶𝐶𝐶𝐶𝐶𝐶 × 𝐶𝐶 (2)
𝐼𝐼

The Lambert – Beer Law combines (1) and (2) into a single equation

𝐼𝐼𝑜𝑜
A = log =ϵCl
𝐼𝐼

where ϵ = absorption coefficient, l = light path, C = Concentration

Eg (1) An aqueous solution of purine triphosphate, at a concentration of 57, 8 mg dm-3 of tri-
sodium dihydrate (molar mass 586 g mol-1), gave an absorbance of 1,014 with a light path of
lens

i. Calculate the molar absorption coefficient

ii. What would be the absorbance of a 10 μM solution, and what would be the percentage
of light transmittance?

Solution: i) A = ϵ C l

𝑨𝑨 𝟏𝟏,𝟎𝟎𝟎𝟎𝟎𝟎
ϵ = 𝒄𝒄 𝒍𝒍 = 𝟓𝟓𝟓𝟓,𝟖𝟖 ×𝟏𝟏𝟏𝟏−𝟑𝟑 (𝒈𝒈/𝒅𝒅𝒅𝒅𝟑𝟑 )
× 1 cm
𝟓𝟓𝟓𝟓𝟓𝟓 (𝒈𝒈/𝒎𝒎𝒐𝒐𝒍𝒍)

= 1,028 × 104 dm3 mol-1 cm-1

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 ii). for a 10 μM solution

A=ϵCl
= 1,028 × (104 dm3 mol-1 cm-1) × 10 × 10-6 (mol dm-3) × 1 cm

= 0,1028
The percentage of light transmittance T% is given by log T% = 2−A
= 2−0,1028
= 1,8972
i.e. T% = 10 1,8972 = 78.9%
Eg. (2) The molar absorption coefficients of human haemoglobin (mol. weight 64000) is 532
dm3 cm-1 mol-1 at 430 nm. A solution of haemoglobin in a cuvette having a light path of 1 cm
was found at that wavelength to have transmittance of 76.7%. Calculate the concentration in
mol dm3 and g dm3. [2,166 × 10-4 mol dm3, 13,86 g dm3]

Atomic Spectra

Atomic spectra may be observed in different regions of the spectrum, depending on energies
involved in electronic transitions.

The splitting of lines in atomic spectra are due to:

I. Coulombic interactions
II. Exchange interactions
III. Spin-orbit interactions

I) Coulombic Interactions

For atoms having more than one electron, there is a significant difference in energy for
electrons having 2nd quantum numbers, eg 2p level higher than 2s level, and 3d above 3p level
and so on …

These differences are due to Coulombic interactions between electrons in atoms. To take into
account the effect of Coulombic interactions, the atomic energy levels are described by capital
letters, called TERM SYMBOLS

 which indicate magnitude of L, the total angular momentum.

for 1e-, orbital angular momentum

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 ℎ
L = �𝑙𝑙(𝑙𝑙 + 1) 2𝜋𝜋

for >1e-, total angular momentum is L = Σ li

ℎ
�𝐿𝐿(𝐿𝐿 + 1) 2𝜋𝜋

where L = 0, 1, 2, 3…, the corresponding term symbols are S, P, D, F…..

The term symbols for hydrogen in its ground and first two excited states is
n=1 l=0 S
n=2 l = 0, 1 S, P
n=3 l = 0, 1, 2 S, P, D
n=4 l = 0, 1, 2, 3 S, P, D, F
Eg (1) Determine the allowed values of L for two electrons in an atom where l1 = l2 = 1 (use
vector addition)

Solution:

⸫ Allowed values are L = 0, 1, 2

Eg (2) Determine the allowed values of L for two electrons in an atom where l1 = 2 and l2 = 1

These allowed values for l : 1, 2 and 3

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II) Exchange Interactions: Multiplicity of States

i. 2nd major cause of splitting after Coulombic interactions, arises from exchange
interaction (or spin correlation)
ii. Effect is due to fact that electrons may be thought of as spinning, and electrons with
same spin interact with one another differently from electrons with opposite spins
1 1
iii. Individual spin quantum numbers are ms = 2 or ms = − 2

Multiplicity = 2S + 1

Examples:

a) ONE ELECTRON b) TWO ELECTRONS

c) THREE ELECTRONS

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NOTE: The multiplicity is indicated in the term symbol as a left hand superscript, i.e. 2S is
read doublet S.
E.g. Determine the possible multiplicities for an atom in the configuration 1s2 2s2 2p2

Solution

Electrons in a complete shell or in completed subshells do not contribute to the total spin in
angular momentum. Therefore, only interactions of the spins of the two p electrons are
considered.

1 1 1 1
mS2 = 2 S=2 +2 =1 mS2 = 2 S=0

Multiplicity = 3 Multiplicity =1
1 1
mS1 = Triplet state mS1 = 2 Singlet state
2

III) Spin orbital interactions

i. These splittings are smaller than those resulting from Coulombic and exchange
interactions between electrons and are due to magnetic coupling between magnetic
moment associated with spin of the electron and magnetic moment associated with
orbital motion of the electron. This coupling is called spin-orbit interaction.
ii. l and s are coupled as; j = l ± S

1
Since ms = ± 2 , for a P state (l = 1), we have two possibilities.

1 3
j = l+S = 1+2 = 2 and

1 1
j = l-S = 1- 2 = 2

iii. Note j is written as a right-hand subscript on the term symbol. i.e. 2P1/2 or 2P3/2
iv. Using vector model

J = L+S

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Pure rotational spectra of molecules

Introduction

1. The energy of an atom can only be electronic energy-and therefore atomic spectra are
due to transitions between different electronic states.
2. Molecular spectra is more complicated- it involves transitions between electronic states
as well as that due to rotational and vibrational energies of molecules.
3. Types of Optical spectra

Spectroscopic Frequency Wavenumbers Energy Types of Information

Region (s-1) (cm-1) (kJ mol-1) Molecular Obtained
Energy
Microwave 109 - 1012 0,03 - 30 4 × 10-4 – Rotation Inter atomic
and far 0,4 distance and
infrared rotational
constant
Infrared 1012 - 1014 30 - 3000 0,4 - 40 Vibration Inter atomic
and rotation distance and
force
constants of
bonds
Visible and 1014 - 1016 3 × 103 – 3 × 40 - 4000 Electronic Electronic
ultraviolet 105 vibration energy
and rotation levels, bond
dissociation
energies,
force
constants of
bonds and
interatomic
distance

4. Pure rotational spectra

i. Rotational transitions only observed if molecule has a dipole moment e. g for linear
molecules with symmetry (no dipole moment) such as N2 and C2H2 – do not have pure
rotational spectrum, whereas those without a centre of symmetry and with dipole moment
such as HF and HCN have a pure rotational spectrum.

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Diatomic molecules

The moment of inertia of a diatomic molecule is calculated in the following way:

The moment about any axes at right angles to the Ƶ axis are equal and are given by;

I = m1r12 + m2r22 (1)

where r1, r2 = represent the distances of the two atomic masses m1 and m2 respectively from the
centre of mass of the molecule.

If r0 is the intermolecular distance, the values of r1 and r2 are given by:

𝑚𝑚2 𝑟𝑟 0 𝑚𝑚1 𝑟𝑟 0
1 2
𝑟𝑟 = �𝑚𝑚 � , 𝑟𝑟 = �𝑚𝑚 �
1 +𝑚𝑚2 1 +𝑚𝑚2

Substitution for r1 and r2 in (1) yields:

2
𝑚𝑚1 𝑚𝑚2 𝑟𝑟0
𝐼𝐼 = � �
𝑚𝑚1 + 𝑚𝑚2

𝐼𝐼 = 𝜇𝜇𝑟𝑟02

Where 𝜇𝜇 = the reduced mass, and for a diatomic molecule is given by:

𝑚𝑚1 𝑚𝑚2
𝜇𝜇 = � �
𝑚𝑚1 + 𝑚𝑚2

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Pure rotational spectra-simple in appearance consisting of equally spaced lines. The energy
difference for the absorption J+1---j between two neighbouring rotation at states-:

∆𝐸𝐸 = 𝐸𝐸𝐽𝐽+1 − 𝐸𝐸𝐽𝐽

ℎ2
= [(𝐽𝐽 + 1)(𝐽𝐽 + 2) − 𝐽𝐽(𝐽𝐽 + 1)] 2
8𝜋𝜋 𝐼𝐼

ℎ2
= 2(𝐽𝐽 + 1)
8𝜋𝜋 2 𝐼𝐼

ℎ2
Frequency 𝜈𝜈 j associated with transitions is 𝜈𝜈j = 2(J + 1) 8𝜋𝜋 2 𝐼𝐼

𝜈𝜈
In terms of wavenumbers (ν¯ = 𝑐𝑐 )

ℎ2
ν¯𝐽𝐽 = 2(𝐽𝐽 + 1) (1)
8𝜋𝜋 2 𝑐𝑐

Can also be written as ν¯𝑗𝑗 = 2(𝐽𝐽 + 1) B¯ (2)

ℎ2
From (1) and (2) B¯ =
8𝜋𝜋2 𝐼𝐼𝑐𝑐

B¯ = rotational constant, h = Planck’s constant, c is the speed of light and I is the moment of
inertia

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 i. The constants 2 B¯ spacing of a pure rotational spectrum is shown in (a)
ii. The linearly increasing energy differences between the corresponding transitions are
shown in (b)

E.g. (1) Absorption by 1H35Cl occurs in the far infrared near ν¯ =200 cm-1, and the spacing
between the neighbouring lines is 20.89 cm-1 find:

a) Rotational constant B¯
b) Moment of inertia
c) Reduced mass
d) Intermolecular distance in 1H35Cl

Solution

∆ν¯ 20.89
a) B¯ = 2
= 2
= 10.445𝑐𝑐𝑐𝑐−1
ℎ2 6.626×10−34 (𝐽𝐽.𝑆𝑆)
b) 𝐼𝐼 = 8𝜋𝜋2 𝑐𝑐 = 8𝜋𝜋2 ×10.445(𝑐𝑐𝑐𝑐−1 )×2.998×1010

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 = 2.680 ×10-47J.s/s-1

= 2.680×10-47kgm2s-2. s/s-1

= 2.680×10-47kgm2

1 𝑀𝑀(𝐶𝐶𝐶𝐶)𝑀𝑀(𝐻𝐻)
c) µ = 𝑁𝑁𝑁𝑁 � � × 10−3 𝑘𝑘𝑘𝑘
𝑀𝑀(𝐶𝐶𝐶𝐶)+𝑀𝑀(𝐻𝐻)
1 35×1
= 6.023×1023 × (35+1 ) × 10−3

=1.627 × 10−27 𝑘𝑘𝑘𝑘

d) I = μ 𝑟𝑟𝑒𝑒2

𝐼𝐼
re = �𝜇𝜇

2,680×10−47
= �1,627×10−27

= 1,283 × 10−10 𝑚𝑚

i.e. the intermolecular distance = 1,283 × 10−10 𝑚𝑚

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