Degenerate Perturbation Theory

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perturbation-theory degeneracy

Core Idea

For degenerate unperturbed levels, solve the matrix eigenvalue problem of H' restricted to the degenerate subspace to find correct zeroth-order states.

Explainer

In regular (non-degenerate) perturbation theory, you found the first-order energy correction E¹ₙ = ⟨n|H'|n⟩ and the first-order state correction by mixing in other unperturbed states. The mixing formula contains terms like ⟨m|H'|n⟩/(E⁰ₙ − E⁰ₘ). This works beautifully when all unperturbed energies are distinct. But what happens when two or more states share the same unperturbed energy? The denominator E⁰ₙ − E⁰ₘ goes to zero, and the formula blows up. Degenerate perturbation theory is the resolution to this breakdown.

The fundamental issue is that when a subspace is degenerate, any linear combination of the degenerate states is an equally valid zero-order eigenstate. The perturbation H' will in general prefer certain combinations — it lifts the degeneracy by having different matrix elements for different basis choices. The correct strategy is to find the good states: those linear combinations of the degenerate subspace that diagonalize H' within that subspace. These good states have well-defined first-order energies and do not suffer from the zero-denominator problem when mixed with states outside the subspace.

Concretely, if you have an n-fold degenerate level with unperturbed states |ψ₁⟩, ..., |ψₙ⟩, you form the n×n degenerate subspace matrix W with elements Wᵢⱼ = ⟨ψᵢ|H'|ψⱼ⟩. Diagonalizing W gives you n eigenvalues — these are the first-order energy corrections — and n eigenvectors — these are the good zeroth-order states. Each eigenvalue E¹ describes how much H' shifts the energy of the corresponding good state. When the n eigenvalues are all different, H' has completely lifted the degeneracy to first order. If some remain equal, you have a residual degeneracy and must look to higher order.

The classic example is the hydrogen atom in an external electric field (the Stark effect). The n = 2 level is four-fold degenerate: the 2s and three 2p states all share the same unperturbed energy. The electric field perturbation H' = eEz mixes these states. Forming the 4×4 matrix and diagonalizing it reveals which combinations are shifted (by ±3eEa₀) and which are unshifted. Crucially, the good states are specific linear combinations of 2s and 2p — not the original spherical harmonics — chosen precisely so that H' is diagonal. Degenerate perturbation theory tells you both how much the levels shift and what the physically relevant quantum states become under the perturbation.

Practice Questions 5 questions

Prerequisite Chain

Counting to 10Counting to 20Understanding ZeroThe Number ZeroCounting to FiveOne-to-One CorrespondenceCombining Small Groups Within 5Addition Within 10Addition Within 20Two-Digit Addition Without RegroupingTwo-Digit Addition with RegroupingAddition Within 100Repeated Addition as MultiplicationMultiplication Facts Within 100Division as Equal SharingDivision as Grouping (Measurement Division)Division: Grouping (Repeated Subtraction) ModelDivision: Fair Sharing ModelDivision as Equal SharingDivision as GroupingBasic Division FactsDivision Facts Within 100Two-Digit by One-Digit DivisionDivision with RemaindersRemainders and Quotients in DivisionDivision Word ProblemsIntroduction to Long DivisionFactors and MultiplesPrime and Composite NumbersEquivalent FractionsRelating Fractions and DecimalsDecimal Place ValueReading and Writing DecimalsComparing and Ordering DecimalsAdding and Subtracting DecimalsMultiplying DecimalsDividing DecimalsDividing FractionsMixed Number ArithmeticOrder of OperationsInteger Order of OperationsVariable ExpressionsCombining Like TermsOne-Step EquationsTwo-Step EquationsSolving Multi-Step EquationsEquations with Variables on Both SidesAngle Pairs: Complementary, Supplementary, and VerticalParallel Lines and TransversalsCorresponding AnglesAlternate Interior AnglesTriangle Angle Sum TheoremExterior Angle TheoremTriangle Inequality TheoremSimilar Triangles: AA SimilaritySimilar Triangles: SSS and SAS SimilarityProportions in Similar TrianglesRight Triangle Trigonometry IntroductionTrigonometric Ratios ReviewRadian MeasureConverting Between Degrees and RadiansThe Unit CircleGraphing Sine and CosineGraphing Tangent and Reciprocal Trigonometric FunctionsDerivatives of Trigonometric FunctionsAntiderivativesIterated Integrals and Fubini's TheoremDouble Integrals in Cartesian CoordinatesDouble Integrals over Rectangular RegionsDouble Integrals in Polar CoordinatesDouble Integrals: Definition and SetupIterated Integrals and Fubini's TheoremDouble Integrals over Rectangular RegionsDouble Integrals over General RegionsApplications of Double Integrals: Area, Mass, and MomentsTriple Integrals in Cartesian CoordinatesTriple Integrals in Cylindrical and Spherical CoordinatesChange of Variables and the Jacobian DeterminantApplications of Triple Integrals: Volume and MassVector Fields and Their RepresentationsLine Integrals of Vector FieldsGreen's TheoremSurface Integrals and Flux of Vector FieldsSurface Integrals and Flux of Vector FieldsDivergence Theorem: Flux and OutflowDivergence TheoremElectric FluxGauss's LawConductors in Electrostatic EquilibriumCapacitance and CapacitorsDielectricsDielectric Constant and Relative PermittivityElectric Field Inside Dielectric MaterialsDielectric Materials and PolarizationDielectric Susceptibility and PermittivityEnergy Density in Electric FieldsElectric Current and Current DensityElectrical Resistance and ResistivityOhm's Law and Circuit ElementsElectromotive Force (EMF) and BatteriesKirchhoff's Circuit Laws: Voltage and CurrentDC Circuit Network Analysis MethodsTransient Response in RC CircuitsRC CircuitsLC and RLC CircuitsAC Circuits: FundamentalsImpedance and ReactanceAC Power and ResonanceElectromagnetic WavesThe Electromagnetic SpectrumBlackbody Radiation and Planck's LawPhotoelectric EffectThe Photon: Light as QuantaCompton ScatteringWave-Particle Dualityde Broglie WavelengthHeisenberg Uncertainty PrincipleWavefunction and the Born RuleThe Schrödinger EquationSolution of the Hydrogen AtomTime-Independent Perturbation TheoryDegenerate Perturbation Theory

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