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Born-Oppenheimer approximation and perturbation theory

Physics Asked by user110503 on November 14, 2021

In the book Molecular Physics by Demtroder there is an explanation of the Born-Oppenheimer approximation and the adiabatic approximation in terms of a perturbative series. The Hamiltonian is $H_0 + T_text{nuc} = H_0 + lambda W$, where $T_text{nuc}$ is the nuclear kinetic energy term. The solutions of $H_0$ are $phi_m(r, R)$ and a general wavefunction is written as a linear combination $psi(r, R) = sum_m chi_m(R) phi_m(r,R)$. The Schroedinger equation $(H_0 + lambda W)psi = Epsi$ is then solved by writing $E$ and $chi_m$ as a series expansion of $lambda$. According to the book, the energy to second order is
$$ E_n = E_n^{(0)} + W_{nn} + sum_{kneq n} frac{W_{nk}W_{kn}}{E_n^{(0)} – E_k^{(0)}}$$
where
$$ W_{nk} = int phi_n^{(0)*} T_text{nuc} phi_k^{(0)} dr.$$

Now I am lost on how this was obtained. They then relate the second term $W_{nn}$ to the adiabatic correction.

Since the energies are labelled, I would assume that then $psi$ would also have to be labelled by $n$.

I would appreciate any suggestions or explanations for this.

Edit: My attempt.

So if I use the $chi$ and $E$ expansion as well as their form of $psi$ then I obtain
$$
(H_0 + lambda W) psi = sum_m chi_m(R) E_m(R) phi_m(r,R) + lambda sum_m phi_m(r,R) W chi_m(R) + chi_m(R) W phi(r,R) = sum_m E chi_m(R)
phi_m(r,R) $$

Now I multiply $phi_k^*(r,R)$ and integrate over $r$ to obtain
$$
E_k(R) chi_k(R) + lambda W chi_k(R) + lambda sum_m chi_m(R) W_{mk} = E chi_k(R).
$$

I should have made clear that in the book the energy was expanded as
$$
E_n = E_n^{(0)} + lambda E_n^{(1)}…$$

Here the energy is labelled so the $psi$ need to be labelled but I will ignore this. If $psi$ is to be normalised then $chi_m(R)^*chi_m(R)$ over $m$ must sum to 1. The zeroth order is then
$$
E^{(0)} = E_k(R)
$$

which is not possible as it depends on $R$. I must be reading something wrong here.

One Answer

Let's apply the fundamentals of perturbation theory. We want to calculate the eigenspectrum of a Hamiltonian. $$ H = H_0 + H' $$

We know the eigenspectrum of the unperturbed Hamiltonian, $H_0 phi_n^0=E_n^0phi_n^0$

The first-order correction to the energy is the expectation value of the of the perturbing operator: $$ E_n^1 = <phi_n^0|lambda W|phi_n^0> $$

See Griffiths for a derivation of first and second order perturbation theory. Griffiths describes the above equation as the most important equation in quantum mechanics. You should see that this is precisely your $W_{nn}$.

Since the energies are labelled, I would assume that then ψ would also have to be labelled by n.

In the adiabatic approximation this is true. An adiabatic perturbation would keep a particle in state n within state n so that $E_n^0->E_n'$ and $phi_n^0->psi_n$. However, it is not true in general. This is why each $psi$ is written as a sum over $phi$

Answered by Tony Ruth on November 14, 2021

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