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How does molecular orbital theory apply to polyatomic molecules?

Here’s a explanation of how Molecular Orbital Theory (MOT) applies to polyatomic molecules:


1. MOT in Polyatomic Molecules

  • In polyatomic molecules (more than two atoms), atomic orbitals from all atoms combine to form molecular orbitals.
  • These molecular orbitals extend over the whole molecule, not just between two atoms.
  • Electrons occupy these MOs according to the Pauli exclusion principle and Hund’s rule, just like in diatomic molecules.

2. Delocalization of Electrons

  • MOT explains electron delocalization in molecules with conjugation or resonance.
  • Example: Benzene (C₆H₆)
    • Six carbon p orbitals combine to form six π molecular orbitals.
    • The π electrons are delocalized over all six carbons, giving resonance stabilization.

3. Predicting Molecular Properties

  • MOT can explain:
    1. Bonding and antibonding interactions in multi-atom systems
    2. Stability (more filled bonding MOs → more stable)
    3. Magnetic properties
      • Molecules with unpaired electrons in MOs are paramagnetic.
      • Molecules with all electrons paired are diamagnetic.
    4. Reactivity
      • HOMO-LUMO interactions help predict where chemical reactions will occur.

4. Example: Water (H₂O)

  • Oxygen has 2s and 2p orbitals; hydrogen has 1s orbitals.
  • All combine to form bonding and antibonding MOs.
  • MOT explains why H₂O has a bent shape and strong O–H bonds, consistent with experimental observations.

5. Key Points

  • MOT for polyatomic molecules uses linear combinations of atomic orbitals (LCAO) to make MOs.
  • Electrons can be delocalized over many atoms, explaining resonance, stability, magnetism, and spectra.

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