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Born Oppenheimer p1-7
Born Oppenheimer p1-7
where the operators in the Hamiltonian are the kinetic energy operators of the nuclei and
the electrons, and then the potential energy operators between the nuclei, between the
electrons, and between the nuclei and electrons. Coordinates are defined below for a three
nucleus, three electron molecule.
1
nuclei 2
Tn = ∑ −2 ∇α
2
α Mα
electrons 2
Te = ∑i=1
−
2 me
∇i
2
nuclei 2
Z Ze
Vnn = ∑∑ α β
α β>α R αβ
electrons 2
e
Vee = ∑i=1
∑
j>i r ij
− Zα e
nuclei electrons
Ven = ∑ ∑
α i riα
There is a repulsive interaction among the nuclear charges and a repulsive charge-charge
interaction among the electrons. However, the interaction potential between electrons and
nuclei is attractive, since the particles have opposite charges. This particular interaction
couples the motions of the electrons and the motions of the nuclei.
The wavefunctions that satisfy this Hamiltonian must be functions of both the
electron position coordinates and the nuclear position coordinates, and this differential
equation is not separable. In principle, true solutions could be found, but this is a
formidable differential equation to work with. An alternative is an approximate (but
generally a very good approximation) separation of the differential equation based upon
the very large difference between the mass of an electron and the masses of the nuclei.
The difference suggests that the nuclei will be sluggish in their motions relative to the
electron motions. Over a brief period of time, the electrons will "see" the nuclei as if fixed
2
in space; the nuclear motions will be relatively slight. The nuclei, on the other hand, will
"see" the electrons as something of a blur, given their fast motions.
b g
ψ ( R , r1 , r2 … ) = ψ ( R 0 , r1 , r2 … ) + R − R 0
∂ψ
+
bR − R0 g 2
∂2 ψ
+…
∂ R R=R
0
2! ∂ R 2 R=R
0
The electron position coordinates are designated r1, r2, etc. We will assume that the
first-derivative term in the expansion is the most important and that the higher order terms
may be neglected. By definition, the first derivative of the wavefunction is
∂ψ
= lim
b g b
ψ R o + δ, r1 , r2 ,… − ψ R o , r1 , r2 ,…g
∂R R = Ro
δ→0 δ
Our physical notion is that the electrons traverse a much greater distance for any
interval of time than do the nuclei because of the mass difference. Therefore, for some
small increment, δ, the electronic elements of the wavefunction will be much more
nearly the same at R = Ro+δ and at R = Ro than will the nuclear elements. This
means that the derivative above is largely determined by the change in the nuclear part of
the wavefunction, and that in turn suggests an approximate separation of the electronic and
nuclear motion parts of the problem.
To make the approximation that the electronic contributions to the derivative above
are zero requires first that the wavefunction be taken to be (approximately) a product of a
function of nuclear coordinates only, φ, and a function of electron coordinates, Ψ,at a
specific nuclear geometry. At the specific nuclear geometry, R = Ro, this is expressed as
ψ ( R o , r1 , r2 ,… ) ≅ φ( R o ) Ψ( R ) ( r1 , r2 ,… )
o
3
ψ ( R o + δ, r1 , r2 ,… ) = φ( R o + δ ) Ψ( R ) ( r1 , r2 ,… )
o
∂ψ φ( R o + δ ) − φ( R o )
= Ψ( R ) ( r1 , r2 ,… ) lim
o
∂R δ
R= R o
δ→0
∂φ
= Ψ ( Ro )
( r1 , r2 ,… )
∂R
R= R o
Of the operators in brackets acting on Ψ (R), only one involves the nuclear position
coordinates. It is the term Ven giving the electron-nuclear attraction potential. In
Ψ(R), the nuclear coordinates are treated as parameters, and we can do the same for
4
Ven, since it acts only on Ψ.
The energy eigenvalue, E, must also have a parametric dependence on the nuclear
positions, as denoted by its superscript. That is, at each different R, there will be a
different Ven, and consequently a different Ψ and a different E.
This is the Schrödinger equation for finding φ. The Hamiltonian consists of a kinetic
energy operator for the nuclear position coordinates, the repulsion potential between the
nuclei, and an effective potential, in the form of E(R), that gives the energy of the electronic
wavefunction as it depends on the nuclear position coordinates.
The sums must be over sets of functions that are complete in the range of the
function f. In a power series expansion; for example, the gi and hi functions would be
polynomials in r and s, respectively. The cij's are the expansion coefficients. In effect, the
Born-Oppenheimer approximation uses such an expansion, but drops all but one term.
The wavefunction is just one product of a function of the nuclear coordinate(s) and a
function of the electron coordinate(s).
We realize that Eq (10) may have a number of different solutions, Just as the
harmonic oscillator has different energy states, the electrons in an atom or molecule may
have different states with different energies available. Also, the nuclear Schrödinger
equation, Eq (12), will have a number of different solutions. The set of these solutions is
complete in the range of the electronic-nuclear wavefunction, Ψ. So in principle, the non-
approximate wavefunction could be written as a sum of product functions,
Ψ = ∑∑c φ ψ
i j
ij i j
We might then say that the system has a nonvanishing probability of being in one or
the other "Born-Oppenheimer state," or that it could be hopping between. Of course, such
a description is entirely within the context of the Born-Oppenheimer approximation since
it presumes a separation of the electronic and nuclear motions. So important is the Born-
Oppenheimer approximation in chemistry that discussions are very often within the
context of the approximation (e.g., separation of electronic and nuclear motion), even if
not stated explicitly.