Limits of Perturbation theory for hydrogenic atoms

In summary, the conversation discusses why perturbation theory cannot be used to calculate the effect of spin-orbit interaction in hydrogen-like uranium. One possible reason is that the perturbation must be small compared to the rest of the Hamiltonian, but for uranium, the ionization energy is still much larger than the spin-orbit shift. Additionally, the Bohr radius for uranium approaches the radius of the nucleus, making the wave function for hydrogen-like uranium invalid. Therefore, using perturbation theory would be redundant and it is more accurate to solve for the wave function using the J operator and other methods.
  • #1
Cheetox
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Homework Statement


Why can't we use perturbation theory to calculate the effect of the spin orbit interaction in hydrogen like uranium?


Homework Equations





The Attempt at a Solution


Is it something to do with the fact that the perturbation must be small compared to the rest of the hamiltonian? But for hydrogen like uranium the ionization energy is still 28000 times that of the spin orbit shift? Or could it be to do with the fact that the bohr radius for uranium approaches the radius of the nucleus?
 
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  • #2
Well, I am a bit confused by your question, too.
So normally, we can obtain the EXACT result by using J operator and what not. And since we can get the exact wave function, why do we want to do it "approximately?"
The reason that Perturbation probably does not work is that, in order to get your energy, you need to know the wave function (or approximately the wave function) through the equation
E_n = <[tex]\Phi[/tex]_n l H l [tex]\Phi[/tex]_n>
We know H, it has many extra terms (especially the L dot S term)
This L dot S term made your previous wave function for Hydrogen invalid.
So without solving J and stuff like that, you actually don't really know what your phi look like (notice that this phi would not look like the original ones, ie, without the spin, because of the L dot S term). So essentially, you still need to go through solving J, and what not. And since you go through the whole thing, you can in fact get the exactly E. So I guess yes you could, it is probably just a bit redundant.
 

1. What is perturbation theory and how does it apply to hydrogenic atoms?

Perturbation theory is a mathematical method used to approximate the solutions to a complex problem by breaking it down into simpler, solvable parts. It is applied to hydrogenic atoms, which have a single electron, to account for small changes or disturbances in the atom's energy levels caused by external forces.

2. What are the limitations of perturbation theory for hydrogenic atoms?

The main limitation of perturbation theory for hydrogenic atoms is that it only works for small changes in the atom's energy levels. If the perturbation is too large, the perturbation theory becomes inaccurate and fails to give a reliable approximation.

3. How does perturbation theory differ from the exact solutions for hydrogenic atoms?

Perturbation theory provides an approximate solution for hydrogenic atoms, while the exact solutions can only be obtained through complex mathematical calculations. The exact solutions take into account all the interactions between the electron and the nucleus, while perturbation theory only considers a small perturbation on top of the unperturbed system.

4. Can perturbation theory be applied to other atoms or molecules?

Yes, perturbation theory can be applied to other atoms or molecules, as long as they have a single electron and the perturbation is small enough. It is commonly used in quantum mechanics to calculate the effects of external forces on the energy levels of atoms and molecules.

5. How accurate is perturbation theory for predicting energy levels in hydrogenic atoms?

The accuracy of perturbation theory for predicting energy levels in hydrogenic atoms depends on the size of the perturbation. For small perturbations, the theory can give very accurate results, but for larger perturbations, the accuracy decreases. In general, perturbation theory provides a good approximation for the energy levels of hydrogenic atoms.

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