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Perturbation-Theory Examples

Perturbation theory turns a solvable problem into an approximation scheme for a nearby problem. A worked example is trustworthy only when it identifies the unperturbed problem, the small parameter, the order kept, and the failure mode.

NeedLearnFormula Check
First-order energy shiftNondegenerate Perturbation TheoryFirst-Order Perturbation Theory
Explicit oscillator correctionAnharmonic Oscillator Perturbationoscillator matrix elements
Degenerate subspaceDegenerate Perturbation Theorydiagonalize perturbation in the degenerate space
Variational estimateHelium Atom Variational EstimateVariational Bound
Time-dependent transitionFermi’s Golden RuleFermi Golden Rule
Semiclassical barrierWKB Barrier TunnelingWKB Quantization

For an unperturbed normalized eigenstate ∣n(0)⟩\lvert n^{(0)}\rangle of H0H_0 and perturbation λV\lambda V, the first-order shift is

En(1)=⟨n(0)∣V∣n(0)⟩.E_n^{(1)} =\langle n^{(0)}\rvert V\lvert n^{(0)}\rangle.

The expression is not the whole method. It assumes a nondegenerate level or a basis already chosen after diagonalizing VV in the degenerate eigenspace.

  • Applying nondegenerate formulas inside a degenerate multiplet.
  • Treating a large correction as a controlled approximation.
  • Forgetting selection rules that make a matrix element vanish.
  • Mixing the perturbation parameter into VV inconsistently.
  • Using WKB through a turning point without the needed connection formula.
  • Treating a variational upper bound as an error estimate by itself.
  • H0H_0 and its known spectrum;
  • perturbation VV and expansion parameter;
  • degeneracy status;
  • order of approximation;
  • symmetry or selection rule;
  • comparison with an exactly solvable or limiting case.
  • R. Shankar, Principles of Quantum Mechanics, 2nd ed., Springer, 1994.
  • J. J. Sakurai and J. Napolitano, Modern Quantum Mechanics, 3rd ed., Cambridge University Press, 2020.
  • C. Cohen-Tannoudji, B. Diu, and F. Laloe, Quantum Mechanics, Wiley, 1977.
  • L. D. Landau and E. M. Lifshitz, Quantum Mechanics: Non-Relativistic Theory, 3rd ed., Pergamon, 1977.
  1. Why is the first-order formula above unsafe for a hydrogenic level with fixed principal quantum number nn?
Solution

The Coulomb spectrum has degeneracies beyond the magnetic quantum number. A perturbation can mix states inside the degenerate subspace, so one must first diagonalize the perturbation restricted to that subspace.