Lecture Note 2: Harmonic Resonance in Molecular Orbitals
1. Introduction
Molecular orbital (MO) theory describes bonding using linear combinations of
atomic orbitals.
Harmonics play a role in understanding standing wave patterns in electron
probability distributions.
Analogy: electrons in orbitals behave like harmonics on a vibrating string.
2. Wavefunctions and Harmonics
Orbitals are solutions of the Schrödinger equation.
Just like a vibrating string, orbitals form standing waves with nodes.
Harmonics correspond to higher quantum states with additional nodes.
3. Hydrogen Atom and Beyond
Hydrogen’s solutions: spherical harmonics Ylm(θ,ϕ)Y_{l}^{m}(\theta,\
phi)Ylm(θ,ϕ).
Quantum numbers:
o nnn: principal (energy level).
o lll: angular momentum (shape).
o mmm: orientation.
Higher nnn values = higher harmonics = more complex nodal structures.
4. Molecular Orbital Harmonics
Bonding orbitals: in-phase overlap → constructive harmonic combination.
Antibonding orbitals: out-of-phase overlap → destructive interference.
Harmonic nature explains stability differences between σ and π bonds.
5. Resonance Analogy
In conjugated systems (e.g., benzene), electrons delocalize across multiple
atoms.
Wavefunctions combine harmonically → standing wave patterns across the
ring.
Explains aromatic stability via cyclic resonance harmonics.
6. Spectroscopic Connections
UV-Vis absorption promotes electrons between harmonic MO levels.
HOMO–LUMO gap corresponds to a fundamental harmonic excitation.
Fluorescence and phosphorescence arise from harmonic relaxation.
7. Applications
Predicting stability of aromatic vs. anti-aromatic systems.
Explaining colors of organic dyes via harmonic delocalization.
Semiconductor band gaps modeled as harmonic-like electron waves.
8. Conclusion
Harmonics are deeply embedded in molecular orbital theory.
Electrons in orbitals behave like standing waves with harmonic resonance
patterns.
This concept unifies physics (wave mechanics) with chemistry (bonding).
