Born–Oppenheimer approximation

1. It is the assumption that the motion of atomic nuclei and electrons in a molecule can be
treated separately, based on the fact that the nuclei are much heavier than the electrons
(more than 1000 times).
2. It leads to a molecular wave function in terms of electron positions r i and nuclear positions Rj.
3. The electronic wavefunction depends upon the nuclear positions R j 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.
4. The nuclear motion (e.g., rotation, vibration) sees a smeared out potential from the speedy electrons.
5. Here we fix R and find  for electrons , and then fix R at another value and do get  and
so on
6. This approximation relies on the observation that the electronic motion is orders of
magnitude faster than the nuclear motion
7. Therefore, the motion of electrons is computed by solving
the electronic Schrödinger equation with nuclei clamped in space.
8. It is the best known mathematical approximation in molecular dynamics.
9.  We had to neglect the effect of the nuclear kinetic energy on the electrons.
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11.
12. Nuclei have much smaller accelerations, so can be taken at rest (but at different
positions) so that different positions of nuclei will lead to different electronic
wavefunctions
13. In the Crude Born-Oppenheimer Approximation , R (positions of nuclei) is set equal
to RoRo, the equilibrium separation of the nuclei, and the electronic wavefunctions are taken to
be the same for all positions of the nuclei.
14. The graph in Figure 10.1.110.1.1 is the
energy of a diatomic molecule as a function of internuclear separation, which serves as the
potential energy function for the nuclei.

15. The equilibrium position of the nuclei is where this function is a minimum, i.e. at R=R0R=R0. If
we obtain the wavefunction at R=R0R=R0, and use this function for all values of RR, we have
employed the Crude Born-Oppenheimer approximation.

16.

17. BO approximation is sometimes called the adiabatic approximation.

18. Adiabatic Approximation: The reaction of a system to a time-dependent perturbation depends in detail on the
time scale of the perturbation._________________ This gradual (slow as compared to say time period of a pendulum)
change in the external conditions characterizes an adiabatic process. The quick movement which had a chaotic effect is
often referred to as sudden.
 In simpler terms, a quantum mechanical system subjected to gradually changing external conditions adapts
its functional form, but when subjected to rapidly varying conditions there is insufficient time for the
functional form to adapt, so the spatial probability density remains unchanged.
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24. Validity/Limitation/Failure: For superconductors, BO fails. Born–
Oppenheimer approximation that allowed us to treat the electronic
and the vibrational properties separately.The second is the
independent electron approximation in which we considered the
properties of one electron in the average potential of all others.3
25. ELECTRON-PHONON INTERACTION IS ALSO IGNORED IN BO APPROXIMATION
(BUT FOR SUPERCONDUCTIVITY, THIS INTERACTION PLAYS T MAJOR ROLE). A possible
mechanism providing a weak attraction between electrons is the interaction between the
electrons and lattice vibrations, the so-called electron– phonon interaction. This
interaction is weak and usually ignored when we use the Born–Oppenheimer
approximation
26. Gf
27. Gfd
28. G
29. g