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Internal and external conversions

  • In the realm of photochemistry and molecular spectroscopy, when a molecule absorbs energy, such as from a photon, it often transitions to an excited electronic state.

  • Once in this excited state, the molecule will undergo processes to return to its ground state.

  • Internal and external conversions are two of these processes that lead to the non-radiative dissipation of the absorbed energy.

Internal Conversion (IC):

  • Internal Conversion is a process where a molecule in an excited electronic state transitions to a lower electronic state without the emission of a photon, but rather by converting the energy into vibrational or rotational energy of the same molecule.

Mechanism:

  • This process is often facilitated by molecular vibrations that are similar in energy to the energy gap between the two electronic states.

  • The excess energy is then redistributed among the molecule's vibrational and rotational modes.

Outcome:

  • The molecule ends up in a higher vibrational level of a lower electronic state (often the ground electronic state).

  • Since vibrational energy is typically rapidly converted to heat through collisions with surrounding molecules, internal conversion often results in the heating of the molecular environment.

External Conversion (EC):

  • External Conversion is a process in which the energy from an excited molecule is transferred to its surroundings without the emission of radiation.

  • This is particularly common when the molecule is in a condensed phase (like in a solid or liquid), where neighbouring molecules or lattice structures can directly interact with the excited molecule.

Mechanism:

  • The vibrational or rotational energy of the excited molecule is directly transferred to the surrounding molecules or lattice, often through collisions or close molecular interactions.

Outcome:

  • The excited molecule returns to its ground state (or a lower excited state), while the surrounding medium gains energy and may increase in temperature.



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