Lecture 3: Degenerate Perturbation Theory

Motivations:

Earlier result based on a non-degenerate assumption:

The perturbed state (here state n) cannot be degenerate with other states in the spectrum. If some degeneracy does occur, then the above first order correction blows up in general We hence need a special treatment for degenerate cases.

Motivations (continued)

If first-order correction diverges, then we may have to worry about what the zeroth-order eigenstate should be

Can we unify non-degenerate perturbation and degenerate perturbation theory under some circumstances?

General remarks on an M-fold degeneracy and the series expansion All with have the same eigenvalue:

So any linear combination of them is also an eigenstate of the same eigenvalue. So what combination can be used as the zeroth-order states? Pondering upon the expansions: 0, then M eigenvalues continuously converge to

0, then a perturbed eigenvector continuously converge to a particular set of eigenstates. Only this set of states (and other non-degenerate states treated as normal) are called zeroth-order eigenstates.

So zeroth-order states must be special superposition states of the degenerate states.

Returning to a previous result from 1st order considerations:

(seen before):

Within the subspace spanned by the M degenerate states

That is: After multiplying any , the above two terms always cancel

Continuing the last side: Hence: Within the degenerate subspace spanned by the M states

where

Thus, in degenerate perturbation theory, the zeroth order states should be the eigenvectors of the perturbation matrix within the degenerate subspace. The associated eigenvalue gives the 1st order correction to the eigen-energy !

Two-fold degeneracy and perturbation

Two basis states of a two-fold degenerate subspace:
matrix elements of the perturbation V:

Example A :

Spin up and spin down are degenerate states in the absence of a magnetic field. The coupling V is induced by a static magnetic field along the x direction.

More examples continued in the next slide

Example B:

A and B have the same energy

AB or BA transitions can now happen.if lowering the central wall

Example C:

Ammonia molecule

Lifting a two-fold degeneracy:

Two basis states of the two-fold degenerate subspace: matrix elements of of the perturbation:

Writing down the Zeroth order eigenstate:

The eigenvector of the V matrix yields the zeroth order eigenstate:

continuing the previous slide:

The splitting occurs even when

Understanding the special case of

The eigenvector of V matrix as the zeroth order eigenstate:

If

then the V matrix is diagonal

1st eigenvector is

i.e.,

with eigenvalue

2nd eigenvector is

i.e.,

with eigenvalue

This leads to an important observation:

For degenerate states under a perturbation, If the off-diagonal matrix elements of the perturbation term are already zero in a certain basis set of the degenerate subspace (that is, that basis set are already the eigenfunctions of V in this subspace), then the zeroth order states are simply these basis states, and the first-order correction to the eigenvalue is simply given by a = 1, 2,

This formula is then identical with that for the non-degenerate case: 1st order correction is given by the expectation value of the perturbation using the zeroth order wavefunction !

Interesting and very useful theorem:

If we find an hermitian operator that commutes with the zeroth order Hamiltonian and the perturbed Hamiltonian:
Both has P-symmetry, Right?

And if the degenerate states are eigenstates of the P operator with different eigenvalues,

Then

=0

so using this set of degenerate states, the first-order correction to the eigenvalue takes the same form as in the non-degenerate perturbation theory.

Simple proof of the theorem:

commutability Taking the inner product with

Since

Example: Bead moving on a circle with a perturbation

radius r mass m coordinate

Two-fold degeneracy:

n and n states have the same eigenvalue

Perturbation is

, with

So this perturbation conserves the parity, just as the Hamiltonian does.

So if we choose
as the basis states of the two-fold degenerate subspace
radius r mass m coordinate

Then the eigenstates

are also eigenstates of the parity operator, with different eigenvalues (+1 and -1). So they belong to different classes of the parity symmetry

Continued on the next slide

Continuing the previous slide:

So if we use the basis states

The perturbation does not couple these two degenerate states, hence first-order energy correction can be evaluated exactly the same way as the non-degenerate perturbation theory:

For example, for the + state:

Summary
For degenerate states, stationary perturbation theory needs a special treatment to yield the correct zeroth order eigenstates. Within each degenerate subspace, the zeroth order eigenstate and the 1st order energy correction are determined by an eigenvalue-eigenstate problem of the perturbing operator. If we can choose a set of basis states such that the perturbation does not have off-diagonal matrix elements in the degenerate subspace, then with that basis set the first order degenerate perturbation theory takes the same form as the non-degenerate case. This observation will be important in treating realistic systems (e.g., hyperfine structure of Hydrogen, treated later). With the zeroth-order states appropriately treated, we can follow previous procedure in non-degenerate cases to find 1st corrections to eigevectors, 2nd corrections to the eigenvalues etc. The results take the same form as before, which can be easily verified. Note however, if the degeneracy is not lifted by our procedure here, then things would be more complicated.