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What is molecular orbital theory (MOT)?

Here’s a explanation of Molecular Orbital Theory (MOT):


1. Definition

  • Molecular Orbital Theory (MOT) explains how atomic orbitals combine to form molecular orbitals when atoms bond together.
  • These molecular orbitals belong to the whole molecule, not just to a single atom.
  • Electrons in these orbitals are spread over the entire molecule rather than being confined between two atoms.

2. Key Points

  1. Combination of Atomic Orbitals (AOs):
    • Atomic orbitals from bonded atoms combine constructively or destructively.
    • Constructive combination → bonding molecular orbital (lower energy)
    • Destructive combination → antibonding molecular orbital (higher energy)
  2. Electron Distribution:
    • Electrons fill molecular orbitals according to:
      • Pauli Exclusion Principle (max 2 electrons per orbital, opposite spins)
      • Hund’s Rule (fill degenerate orbitals singly first)
  3. Types of Molecular Orbitals:
    • Bonding (σ, π) → stabilize the molecule
    • Antibonding (σ, π)** → destabilize the molecule
    • Non-bonding (n) → electrons stay on one atom, neither stabilizing nor destabilizing

3. Importance of MOT

  • Explains bond order (strength and stability of bonds)
  • Predicts magnetic properties (paramagnetic vs diamagnetic)
  • Explains electron delocalization in molecules with resonance
  • Helps understand spectroscopy and chemical reactivity

Example:

  • In H₂, the 1s orbitals of two hydrogen atoms combine to form:
    • A σ₁s bonding orbital → electrons stabilize the molecule
    • A σ*₁s antibonding orbital → empty in H₂, so it doesn’t destabilize

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