Consider, for example, a Hamiltonian which is separable into two
terms, one involving coordinate *q*_{1} and the other involving coordinate
*q*_{2}.

(135) |

with the overall Schrödinger equation being

(136) |

If we assume that the total wavefunction can be written in the form , where and are eigenfunctions of and with eigenvalues

= | (137) | ||

= | |||

= | |||

= | |||

= |

Thus the eigenfunctions of are products of the eigenfunctions of and , and the eigenvalues are the sums of eigenvalues of and .

If we examine the nonrelativistic Hamiltonian (134), we
see that the term

(138) |

prevents us from cleanly separating the electronic and nuclear coordinates and writing the total wavefunction as , where represents the set of all electronic coordinates, and represents the set of all nuclear coordinates. The Born-Oppenheimer approximation is to assume that this separation is nevertheless

Qualitatively, the Born-Oppenheimer approximation rests on the fact that the nuclei are much more massive than the electrons. This allows us to say that the nuclei are nearly fixed with respect to electron motion. We can fix , the nuclear configuration, at some value , and solve for ; the electronic wavefunction depends only parametrically on . If we do this for a range of , we obtain the potential energy curve along which the nuclei move.

We now show the mathematical details. Let us abbreviate the molecular
Hamiltonian as

where the meaning of the individual terms should be obvious. Initially, can be neglected since is smaller than by a factor of

(140) |

such that

This is the ``clamped-nuclei'' Schrödinger equation. Quite frequently is neglected in the above equation, which is justified since in this case is just a parameter so that is just a constant and shifts the eigenvalues only by some constant amount. Leaving out of the electronic Schrödinger equation leads to a similar equation,

(142) |

where we have used a new subscript ``e'' on the electronic Hamiltonian and energy to distinguish from the case where is included.

We now consider again the original Hamiltonian (139).
If we insert a wavefunction of the form
,
we obtain

(144) |

Since contains no dependence,

(146) |

However, we may not immediately assume

(147) |

(this point is tacitly assumed by most introductory textbooks). By the chain rule,

(148) |

Using these facts, along with the electronic Schrödinger equation,

(149) |

we simplify (145) to

(150) | |||

= |

We must now estimate the magnitude of the last term in brackets.
Following Steinfeld [5], a typical contribution has
the form
,
but
is of the
same order as
since the derivatives operate over
approximately the same dimensions. The latter is
,
with *p*_{e} the momentum of an electron. Therefore
.
Since
,
the term in brackets can be dropped, giving

(151) |

(152) |

This is the nuclear Shrodinger equation we anticipated--the nuclei move in a potential set up by the electrons.

To summarize, the large difference in the relative masses of the
electrons and nuclei allows us to approximately separate the
wavefunction as a product of nuclear and electronic terms. The
electronic wavefucntion
is solved for a given set of nuclear
coordinates,

(153) |

and the electronic energy obtained contributes a potential term to the motion of the nuclei described by the nuclear wavefunction .

(154) |

As a final note, many textbooks, including Szabo and Ostlund
[4], mean total energy *at fixed geometry* when
they use the term ``total energy'' (i.e., they neglect the nuclear
kinetic energy). This is just *E*_{el} of equation (141),
which is also *E*_{e} plus the nuclear-nuclear repulsion. A somewhat
more detailed treatment of the Born-Oppenheimer approximation is given
elsewhere [6].