The Stark Effect for n=2 Hydrogen.

The Stark effect for the n=2 states of hydrogen requires the use of degenerate state
perturbation theory since there are four states with (nearly) the same energies. For our
first calculation, we will ignore the hydrogen fine structure and assume that the four

states are exactly degenerate, each with unperturbed energy of . That

is . The degenerate states ,

, , and .

The perturbation due to an electric field in the z direction is . So

our first order degenerate state perturbation theory equation is

This is esentially a 4X4 matrix eigenvalue equation. There are 4

eigenvalues , distinguished by the index .

Because of the exact degeneracy

, and can be eliminated from the equation.

This is just the eigenvalue equation for which we can write out in
(pseudo)matrix form

Now, in fact, most of the matrix elements of are zero. We will show that

because , that all the matrix elements between states of

unequal are zero. Another way of saying this is that the operator z doesn't
``change'' . Here is a little proof.
This implies that unless .

Lets define the one remaining nonzero (real) matrix element to be .

The equation (labeled with the basis states to define the order) is.

We can see by inspection that the eigenfunctions of this operator are

, , and with eigenvalues (of ) of 0, 0,

and .
What remains is to compute .

Recall and .

This is first order in the electric field, as we would expect in first order (degenerate)
perturbation theory.
If the states are not exactly degenerate, we have to leave in the diagonal terms

of . Assume that the energies of the two (mixed) states are ,

where comes from some other perturbation, like the hydrogen fine structure.

(The and are still not mixed by the electric field.)

This is OK in both limits, , and . It is also correct when the

two corrections are of the same order.

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