Molecular spectroscopy

 What can happen when photon incident on a molecule or atom?

𝜆𝜈 = 𝑐
 What is photon?
𝜈 1
 Electromagnetic wave 𝜈= =
𝑐 𝜆

𝐸(𝑥, 𝑡) = 𝐸0 cos 2𝜋𝜈𝑡 − (2 𝜋 𝜆)𝑥 + 𝜙

𝐵(𝑥, 𝑡) = 𝐵0 cos 2𝜋𝜈𝑡 − (2 𝜋 𝜆)𝑥 + 𝜙

 Quantization of Energy Levels

Particle Confined in a Box

𝑛2 ℎ2 Classically
𝐸𝑛 = Allowed
8𝑚𝐿2

𝑛 = 1, 2, 3, …

2
 Quantization of Electronic Energy Levels

Electron Confined in a Atom

𝑍 2 𝜇𝑒 4
𝐸𝑛 = −
32𝜋 2 𝜀02 ħ2 𝑛2
𝑛 = 1, 2, 3, … (𝑃𝑟𝑖𝑛𝑐𝑖𝑝𝑎𝑙 𝑄𝑢𝑎𝑛𝑡𝑢𝑚 𝑁𝑢𝑚𝑏𝑒𝑟
Electronic Energy Levels)

𝑍 − 𝐴𝑡𝑜𝑚𝑖𝑐 𝑁𝑢𝑚𝑏𝑒𝑟

𝜇 − 𝑅𝑒𝑑𝑢𝑐𝑒𝑑 𝑀𝑎𝑠𝑠
ℎ
ħ= , 𝑤ℎ𝑒𝑟𝑒 ℎ 𝑖𝑠 𝑃𝑙𝑎𝑛𝑐𝑘 ′ 𝑠 𝐶𝑜𝑛𝑠𝑡𝑎𝑛𝑡
2𝜋

𝜀0 − 𝐷𝑖𝑒𝑙𝑒𝑐𝑡𝑟𝑖𝑐 𝑃𝑒𝑟𝑚𝑖𝑡𝑡𝑖𝑣𝑖𝑡𝑦

Above solution is valid for only

one electron system.
3
 Quantization of Vibrational Energy Levels

Harmonic Oscillator

1
𝐸𝑣 = 𝑣 + ħ𝜔
2

𝑣 = 0, 1, 2, 3, … (𝑉𝑖𝑏𝑟𝑎𝑡𝑖𝑜𝑛𝑎 𝑄𝑢𝑎𝑛𝑡𝑢𝑚
Number)
1 2
𝑘𝑓
𝜔= − 𝐴𝑛𝑔𝑢𝑙𝑎𝑟 𝑓𝑟𝑒𝑞𝑢𝑒𝑛𝑐𝑦
𝑚

ℎ
ħ= , 𝑤ℎ𝑒𝑟𝑒 ℎ 𝑖𝑠 𝑃𝑙𝑎𝑛𝑐𝑘 ′ 𝑠 𝐶𝑜𝑛𝑠𝑡𝑎𝑛𝑡
2𝜋

4
 Quantization of Rotational Energy Levels

Rigid Rotor

ħ2
𝐸𝐽 = 𝐽 𝐽 + 1
2𝐼

𝐽 = 0, 1, 2, 3, … (𝑅𝑜𝑡𝑎𝑡𝑖𝑜𝑛𝑎𝑙 𝑄𝑢𝑎𝑛𝑡𝑢𝑚
Number)

Note that the energy separation between

neighbouring levels increases as J increases.

5
 The energy of a molecule, atom, or subatomic particle that is confined to a
region of space is quantized, or restricted to certain discrete energy values.

 What happens to quantization for particles with large mass or large container?
𝐸𝑛 = 𝑛2 ℎ2 8𝑚 𝐿2
 Consequently, quantization is very important for electrons in atoms and
molecules, but usually unimportant for macroscopic bodies.
0.01 kJ mol-1 10 kJ mol-1 103 kJ mol-1