# Full Hamiltonians

1. Aug 6, 2013

Wikipedia distinguishes between the full "Molecular Hamiltonian" and the "Coulomb Hamiltonian" with which you solve the Schrodinger equation here: http://en.wikipedia.org/wiki/Molecular_Hamiltonian.

how is full molecular Hamiltonian written for a H nucleus and electron or H2 molecule?

2. Aug 22, 2013

### Staff: Mentor

You usually do not use the full molecular Hamiltonian, but add relativistic corrections, such as spin-orbit coupling, to the Coulomb Hamiltonian.

Actually, I'm not sure that would be such a thing as the "full" molecular Hamiltonian. You would use the Dirac instead of the Scrhödinger equation to get all relativistic effects to be taken into account.

3. Aug 22, 2013

If you see the Hamiltonian specified on page 3 here: http://www.phys.ubbcluj.ro/~vchis/cursuri/cspm/course2.pdf

What would I add to that to make it as exact as we know how to make it? That is, if relativistic corrections are reasonably easy to make. Spin-orbit coupling is a purely relativistic effect?

4. Aug 22, 2013

### Staff: Mentor

If you start from the Dirac equation for one electron and assume that relativistic effects are small, you can obtain a series expansion in terms of $v/c$ that you can use as corrective terms (or perturbation) in the Hamiltonian for the hydrogen atom. Spin-orbit coupling is one of those terms. Actually, you get (assuming a fixed nucleus)
$$\hat{H} = m_e c^2 + \frac{\hat{P}^2}{2m_e} + V(R) - \frac{\hat{P}^4}{8 m_e^3 c^2} + \frac{1}{2 m_e^2 c^2} \frac{1}{R} \frac{d V(R)}{dR} \hat{L} \cdot \hat{S} + \frac{\hbar^2}{8 m_e^2 c^2} \Delta V(R) + \ldots$$