Perturbation Theory (stationary)
Lecture 2: Non-degenerate perturbation theory and sample applications
Lecture 3: Degenerate perturbation theory and sample applications
Lecture 4: Fine structure of Hydrogen atom Lecture 5: Weak-field Zeeman effect and hyperfine splitting
Lecture 2: Stationary Perturbation Theory
(non-degenerate cases)
Given an exactly solvable Hamiltonian with eigenkets and eigen-energies
Can we say something about the perturbed system
Standard trick here: Power series expansion of the unknown solution in terms of the perturbation strength
Unknown solution:
Known solution:
Assume
is a smooth function of
Assume
is a smooth function of
Some remarks on the series expansion:
When 0,
the solution should smoothly approach the known solution at = 0
One can assume that the correction terms are orthogonal to the zeroth-order term. If not, we can add those components parallel to the zeroth-order term and then get the same expression after requesting the coefficient of the zeroth-order term to be unity (eigenfunction multiplied by any factor remains eigenfunction).
Normalization is okay up to the second order, so re-nomarlization might be needed depending what order of accuracy is desired.
Some plug-ins and term-by-term comparisons:
Zeroth order term of : 1st order term of :
2nd order term of :
looks messy, but still okay
One more step in working out the approximate solution
Project the obtained equations onto the basis set
(you have to adopt a representation to do something specific)
1st order:
2nd order:
(these two expressions come from the last slide)
1st order correction to the eigenket: Nondegenerate cases
1st order:
Multiply both sides by
with m = n :
Continued on the next slide
Continuing the last slide:
If the unperturbed system is nondegenerate:
Inserting completeness condition:
1st order correction to the eigenvalue: Nondegenerate cases
Multiply both sides by
Remark:
1st order correction to eigenvalue is given by the expectation value of the perturbation on zeroth-order eigenstates
Simple derivation of Feynman-Hellmann Theorem
perturbed Hamiltonian: polynomial expansion: 1st order eigenvalue :
shifting this result to arbitrary
Feynman-Hellmann Theorem
Example A: Perturbation to a harmonic potential
harmonic oscillator perturbation
Recall Virial theorem Or equal partition of a harmonic oscilator system:
The parameter in our perturbative treatment is now represented by epsilon here
Example B: two identical bosons in an infinite square well
Perturbation:
Zeroth order ground state:
2nd order correction to the eigenvalue: Nondegenerate cases
2nd order:
Multiply both sides by
Comments on 2nd order correction to the eigenvalue
The 2nd order correction is given by the overlap between the 1st order eigenket, the perturbation, and the zeroth-order eigenket.
The 2nd order correction reflects the curvature of the eigenvalue (i.e., 2nd order derivative) as a function of the perturbation strength. Small energy level spacings lead to large curvatures of the energy curves.
Example C: 2nd order corrections in a perturbed harmonic oscillator system
harmonic oscillator perturbation
=0
Continuing the previous slide:
summation index
mass
Because of the special form the perturbation, all higher-order corrections are zero !
Summary
Power series expansion is used to obtain perturbative solutions of the stationary Schrodinger equation. If the zeroth order spectrum is nondegenerate, up to 2nd order results are explicitly given.
If the zeroth order spectrum is degenerate, then our 1st order eignestates are in trouble (why?) and hence we have yet to find a special treatment for degenerate cases (topic of next lecture).