Quantum Chemistry

Lecture 6

Dr. Rohul Hayat Adnan

Department of Chemistry UTM
Physics is becoming
too difficult for
physicists
- David Hilbert
(mathematician
 Classical Harmonic Oscillator

• Imagine a mass, m, attached to a spring

that oscillates up and down
• The force of oscillation, F = -kx
• The potential energy, V
1
𝑉 = − ‫ 𝑥𝑘 = 𝑥𝑑 𝐹 ׬‬2
2
• Angular frequency
𝑘
𝜔= = 2𝜋𝑓
𝜇
 Quantum Harmonic Oscillator
ℏ2 𝑑 2 𝜓
• Write down the TISE: − + 𝑉𝜓 = 𝐸𝜓
2𝑚 𝑑𝑥 2
• The potential energy, V
1
𝑉 = 𝑘𝑥 2
2
ℏ2 𝑑 2 𝜓
• The TISE then becomes − + 𝑉𝜓 = 𝐸𝜓
2𝑚 𝑑𝑥 2
2
• The WF takes the form 𝜓 𝑥 = 𝐴𝑛 𝐻𝑛 𝑥 𝑒 −𝛼𝑥

Normalization Gaussian function

constant
Hermite polynomial
• Boundary conditions: 𝜓 𝑥 → 0 𝑎𝑠 𝑥 → ±∞
1 1
• Energy level, 𝐸𝑛 = 𝑛 + ℏ𝜔 = 𝑛 + ℎ𝑓
2 2
 Summary - Quantum Harmonic Oscillator
1
• Energy level 𝐸𝑛 = 𝑛 + ℏ𝜔 (cf. for
2 2 2
2
𝑛 𝜋 ℏ
particle in a box 𝐸𝑛 =
2𝑚𝐿2
• Consistent with energy level of emission
from blackbody (∆𝐸 = ℏ𝜔)
• Energy level of ground state, n=0, is 𝐸 =
1
ℏ𝜔
2
• The energy levels are equally space
• The #nodes = quantum no.
 Exercise
• Calculate the frequency of vibration and energy level spacing for 1H35Cl
molecule
Hint: Mass of H = 1.0078 amu, Mass of Cl = 34.9688 amu, k = 480 N/m
• A hydrogen atom is adsorbed on the surface of gold nanoparticles by a
bond force constant of 855 N/m. Calculate its zero-point vibrational energy
• Strongest IR band for 12C16O occurs at ν = 2143 cm-1. Find the force
constant.
Hint: mass of C = 12 amu, mass of O = 15.995 amu
 Morse Potential
• HO cannot represent vibration of real
systems because bonds break at high
energy
• Only GS is well-represented by HO
• Better model is to use Morse Potential
that include anharmonicity of vibration
1 1
𝐸𝑣𝑖𝑏 = 𝑛+ ℎ𝑓𝑒 − 𝑛 + ℎ𝑓𝑒 𝑥𝑒
2 2