Long time ago, we talked about the mean-field calculation, an touched Hartree-Fock method. In that time, we explained excited-state approach. Now, we explain another approach by variation of the wave functions. This approach is inevitable in atomic physics, because the potential is fixed.

The Hamiltonian is

H = H_1 + H_2 + V_{12}

Since the spin component is anti-parallel, the space part of the total wave function is

\Psi = \phi_1(r_1) \phi_2(r_2)

The Schrodinger equation is

H\Psi = E\Psi

Integrate both side with \phi_1(r_1)

\int dr_1 \phi_1(r_1) H \Psi = \int dr_1 \phi_1(r_1) E \Psi

using the normalization and define \left<x| 1\right> = \phi_1(r_1)

\left<1|H|1\right> \phi_2(r_2) = E \phi_2(r_2)

similarly

\left<2|H|2\right> \phi_1(r_1) = E \phi_1 (r_1)

expand H = H_1 + H_2 + V_{12}

(H_2 + \left<1|V_{12}|1\right>) \phi_2(r_2) = (E - \left<1|H_1|1\right>) \phi_2(r_2)

(H_1 + \left<2|V_{12}|2\right>) \phi_1(r_1) = (E - \left<2|H_2|2\right>) \phi_1(r_1)

Now, we have 2 equations,  an initial guess of \Psi = \phi_1(r_1) \phi_2(r_2) ,

The difficulty is that, the \left<1|V_{12}|1\right> contains 2 variables.

Capture.PNG

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