The Born-Oppenheimer Approximation

The Born-Oppenheimer Approximation is the assumption that the electronic motion and the nuclear motion in molecules can be separated. It leads to a molecular wave function in terms of electron positions ri and nuclear positions Rj.

This involves the following assumptions

  • The electronic wavefunction depends upon the nuclear positions Rj but not upon their velocities, i.e., the nuclear motion is so much slower than electron motion that they can be considered to be fixed.
  • The nuclear motion (e.g., rotation, vibration) sees a smeared out potential from the speedy electrons.


Molecular spectra concepts
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