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Electronic transitions & Types of Electronic Transitions

Definition

  • Electronic transitions refer to the movement of electrons between different energy levels within a molecule upon absorption of light.

  • In UV-Visible spectroscopy, these transitions typically include:

1) π → π*:

  • Electrons in pi bonds (π bonds) are excited to anti-bonding pi-star (π*) orbitals.

2) n → π*:

  • Non-bonding electrons (n electrons), often lone pairs on heteroatoms like oxygen or nitrogen, are excited to anti-bonding pi-star (π*) orbitals.

3) σ → σ*:

  • Electrons in sigma bonds (σ bonds) are excited to anti-bonding sigma-star (σ*) orbitals.

  • These transitions generally require higher energies (shorter wavelengths) compared to π → π* or n → π* transitions.

Energy Levels

Ground State:

  • The lower energy state of the molecule, where electrons are in their stable, unexcited state.

Excited State:

  • The higher energy state reached after electrons absorb energy and move to higher orbitals.

Selection Rules of Electronic transitions

  • Not all electronic transitions are permitted. The likelihood of a transition depends on certain selection rules:

Allowed Transitions:

  • Transitions that typically involve a change in dipole moment, e.g., π → π* and n → π*.

Forbidden Transitions:

  • Transitions that do not involve a change in dipole moment; for example, those occurring between orbitals of the same symmetry.

  • These transitions are less likely or weaker in intensity.


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