
Advanced Quantum Mechanics course sequence · Interactive lesson
The operator K = β(Σ⋅L + ħ) and the quantum number κ
Once α⋅p mixes an s wave with a p wave, l is no longer a quantum number, and every level diagram needs a new label. This topic builds Dirac's operator K, proves it is conserved, and turns its eigenvalue into the integer κ that every relativistic atomic calculation, from hydrogen to uranium, uses to name an orbital.
UAQM-07.02 · Lesson 2 of 9 in this unit. Position is not a completion score.Build the model
When l stops being conserved, one integer takes over j and parity together.
The key idea
κ is the non-zero integer defined by Kψ = −κħψ, where K = β(Σ⋅L + ħ) is Dirac's conserved operator: |κ| = j + ½, and its sign says whether the upper component has l = j − ½ (κ < 0) or l = j + ½ (κ > 0).
Example. Hydrogen's 1s₁/₂ state has κ = −1: K returns +ħ = 1.05 × 10⁻³⁴ J s, j = |κ| − ½ = ½, the upper pair is an s wave and the lower a p wave. 2p₁/₂ has κ = +1 and 2p₃/₂ has κ = −2, although both upper pairs have l = 1.
The complete physical model and assumptions
In a central field the Dirac Hamiltonian H = cα⋅p + βmc² + V(r) conserves J and parity but not L², because the odd operator α⋅p moves amplitude between the upper and lower pairs and shifts the orbital label by one. Every bound state is two orbital waves at once, l above and l′ = l ± 1 below, so a level needs a new name. Dirac's operator K = β(Σ⋅L + ħ) supplies it. Σ⋅L + ħ anticommutes with α⋅p, the +ħ being exactly what cancels the anticommutator of Σ⋅L, and β anticommutes with it too; the two sign flips cancel, while β and V(r) commute with both factors, so K is conserved. Its square is J² + ħ²/4, so its eigenvalues are ±(j + ½)ħ, written −κħ with κ a non-zero integer. On the upper pair K is Quantum Mechanics II's spin-orbit operator 2S⋅L/ħ + ħ, which fixes the sign: κ = −(l + 1) when j = l + ½ and κ = +l when j = l − ½. On the lower pair β reverses Σ⋅L + ħ, and that is what forces the pair onto the other orbital value. One integer now carries j through |κ| and parity through its sign. The label is only as good as the symmetry behind it: K survives any rotationally invariant potential, vector or scalar, but a magnetic field mixes κ = +1 with κ = −2, hyperfine coupling makes F the good label, and in a many-electron atom κ is exact only in the central-field model. And κ names a level without fixing its energy; that takes the radial equations.
1Why l has to be replaced
Work in SI units with the Dirac representation, β = diag(1, 1, −1, −1) and α carrying σ off the diagonal; the metric is (+, −, −, −), though nothing here needs a four-vector. For H = cα⋅p + βmc² + V(r), topic 7.01 showed that J = L + ħΣ/2 and the Dirac parity γ⁰P commute with H while L² and S⋅L do not. α⋅p is odd, so it moves amplitude between the upper and lower pairs, and as a vector operator it changes l by one. A state of definite j and parity therefore has two orbital labels, l above and l′ = l ± 1 below, and l names neither the state nor its energy. J² and parity still sort the states; what is wanted is a single conserved operator whose eigenvalue does that sorting in one number and can stand in the radial equations. Dirac's answer in 1928 was K = β(Σ⋅L + ħ). It is a rotational scalar, so [K, J] = 0, and it is unchanged by inversion, because Σ and L are axial vectors and β commutes with γ⁰ = β.
2Two sign flips make K commute with H
Write Λ = Σ⋅L + ħ, so K = βΛ; β is block-diagonal and commutes with Σ and L, so K = Λβ too. The kinetic term is odd: βα⋅p = −α⋅pβ. In the Dirac representation α = γ⁵Σ, with γ⁵ the off-diagonal identity blocks, which commute with Σ, so Λ anticommutes with α⋅p if σ⋅L + ħ anticommutes with σ⋅p. The Pauli identity (σ⋅a)(σ⋅b) = a⋅b + iσ⋅(a × b) gives (σ⋅L)(σ⋅p) + (σ⋅p)(σ⋅L) = L⋅p + p⋅L + iσ⋅(L × p + p × L). Here L⋅p = p⋅L = 0 and L × p + p × L = 2iħp, so that anticommutator is −2ħσ⋅p, and the +ħ adds +2ħσ⋅p: the sum vanishes, which is why the ħ is there. Then Kα⋅p = βΛα⋅p = −βα⋅pΛ = α⋅pβΛ = α⋅pK. β commutes with K, and V(r) commutes with L, Σ and β, so [K, H] = 0, derived, for any central V. Dimensions: K is in J s, like L. Free-field limit: with V = 0 nothing changes, so free spherical waves carry κ as well.
3K² = J² + ħ²/4 fixes the size of κ
Since β² = 1 and β commutes with Λ, K² = Λ² = (Σ⋅L)² + 2ħΣ⋅L + ħ². The Pauli identity again, with L × L = iħL, gives (Σ⋅L)² = L² + iΣ⋅(iħL) = L² − ħΣ⋅L, so K² = L² + ħΣ⋅L + ħ². Expanding J² = (L + ħΣ/2)² = L² + ħΣ⋅L + 3ħ²/4, because Σ⋅Σ = 3, gives K² = J² + ħ²/4, derived; both sides are in J² s². On a state of total angular momentum j the eigenvalue is ħ²[j(j + 1) + ¼] = (j + ½)²ħ², a perfect square, so K = ±(j + ½)ħ. The convention writes the eigenvalue as −κħ, and κ runs over ±1, ±2, ±3 and so on; κ = 0 would need j = −½, which no state has. For j = ½ the choices are K = ±ħ, for j = 3/2 they are ±2ħ. K² cannot say which sign a given state takes. That needs K itself, evaluated where it is simplest.
4On the upper pair K is the spin-orbit operator
Where β = +1, K = σ⋅L + ħ = 2S⋅L/ħ + ħ, with S = ħσ/2: Quantum Mechanics II's spin-orbit operator, doubled, divided by ħ and shifted by ħ. In QM-II's coupled state |l, ½, j, mⱼ⟩, 2S⋅L/ħ = ħ[j(j + 1) − l(l + 1) − ¾], which is lħ for j = l + ½ and −(l + 1)ħ for j = l − ½. So K = (l + 1)ħ = (j + ½)ħ on the first branch and −lħ = −(j + ½)ħ on the second, and with Kψ = −κħψ, κ = −(l + 1) for j = l + ½ and κ = +l for j = l − ½, derived. s₁/₂ is −1, p₁/₂ is +1, p₃/₂ is −2, d₃/₂ is +2 and d₅/₂ is −3. Read backwards, S⋅L = −(κ + 1)ħ²/2 on the upper pair: 0 for s₁/₂, −ħ² for p₁/₂, +ħ²/2 for p₃/₂, the values QM-II found. Non-relativistic limit: the upper pair becomes the Pauli spinor, so κ is QM-II's (l, j) relabelled and nothing about a slow electron changes.
5The lower pair, parity, and one integer for both
Where β = −1, K = −(σ⋅L + ħ), so to give the same eigenvalue −κħ the lower pair needs σ⋅L + ħ = +κħ: the coupled state of the same j on the other branch, with orbital label l′ = 2j − l. For 1s₁/₂, κ = −1 and l′ = 1, so the small component of the ground state is a p wave. Compactly, l(l + 1) = κ(κ + 1) and l′(l′ + 1) = κ(κ − 1): the lower pair of κ has the angular form of the upper pair of −κ, which topic 7.03 builds explicitly. The Dirac parity γ⁰P gives the upper pair (−1)l and the lower −(−1)(l′), which equals (−1)l because l′ = l ± 1, so the state has parity (−1)l = sgn(κ)(−1)κ. At fixed j the two signs of κ are the two parities, and |κ| is j + ½: κ carries j and parity together. l alone cannot do this, because l = 1 belongs both to κ = +1, p₁/₂, and to κ = −2, p₃/₂.
6Sign conventions, and what the measured spectrum says
This course's Kψ = −κħψ is the convention of Rose's Relativistic Electron Theory, Sakurai and Greiner, and gives the same κ as Johnson's Atomic Structure Theory, which reaches it through a different but equivalent operator: κ = −1 for s₁/₂, which is also how relativistic atomic-structure codes such as GRASP label orbitals. Papers on the hidden symmetries of the Dirac-Coulomb problem, such as Khelashvili and Khachidze's or Al-Hashimi, Shalaby and Wiese's, label states by the eigenvalue of K/ħ itself, making s₁/₂ +1 and p₁/₂ −1, and every sign-dependent formula, the radial equations included, flips with it. Test any borrowed formula on 1s, where it must give l = 0. Hydrogen's measured n = 2 levels back the label. 2P₁/₂ and 2P₃/₂ share l = 1 but differ in |κ|, and lie 10.969 GHz apart. 2S₁/₂ and 2P₁/₂ differ in l and in the sign of κ but share |κ| = 1, and lie only 1.058 GHz apart, a Lamb shift Unit 13 computes. The Dirac energy depends on n and |κ| alone, which topic 7.06 derives and this lesson only quotes.
Key equations
Read the units, assumptions and limits before substituting.
Dirac's operator K
K = β(Σ⋅L + ħ) = β(Σ⋅J − ħ/2)
A rotational scalar, unchanged by inversion, that survives the coupling of upper and lower pairs by α⋅p where L² and S⋅L do not.
β = diag(1, 1, −1, −1) and Σ = diag(σ, σ) are dimensionless 4 × 4 matrices; L and J = L + ħΣ/2 in J s, so K is in J s.Conserved in any central field
[K, H] = 0 for H = cα⋅p + βmc² + V(r)
Two sign flips cancel as α⋅p passes β and then Σ⋅L + ħ, so K labels the stationary states of any central V, Coulomb or not.
Because β and Σ⋅L + ħ each anticommute with α⋅p, while β and V(r) commute with Σ⋅L + ħ. V is in J. Derived here.The square of K
K² = J² + ħ²/4
A perfect square, so K = ±(j + ½)ħ: every eigenvalue is a non-zero integer multiple of ħ, and K = 0 cannot occur.
Both sides in J² s². On a state of total angular momentum j the eigenvalue is (j + ½)²ħ². Derived here.The quantum number κ
Kψ = −κħψ, κ = −(j + ½) for j = l + ½ and κ = +(j + ½) for j = l − ½
One integer fixes j = |κ| − ½ and, through its sign, the branch and the parity, so κ replaces l as the name of a level.
κ is a dimensionless non-zero integer; l is the upper pair's orbital label. s₁/₂: −1, p₁/₂: +1, p₃/₂: −2, d₃/₂: +2. Derived here.Upper orbital label from κ
l(l + 1) = κ(κ + 1)
Both branches in one formula, and the parity follows as (−1)l = sgn(κ)(−1)κ, opposite for the two signs of κ at fixed j.
l dimensionless: l = κ if κ > 0, −κ − 1 if κ < 0. The lower pair takes κ → −κ: l′(l′ + 1) = κ(κ − 1), so l′ = 2j − l. Derived here.Spin-orbit eigenvalue on the upper pair
S⋅L = −(κ + 1)ħ²/2
Quantum Mechanics II's spin-orbit eigenvalue in one line: 0 for s₁/₂, −ħ² for p₁/₂ and +ħ²/2 for p₃/₂, the input to fine structure.
S = ħσ/2 and L in J s, so S⋅L in J² s². Holds where β = +1, on which K = 2S⋅L/ħ + ħ. Derived here.Interactive lab
Predict first. Explore the model. Compare the result.
Explore the model
Try this. Hold j at 1.5 and flip the sign: κ = −2 is P₃/₂ and κ = +2 is D₃/₂, and the filled and open dots trade heights, because the lower pair of κ is the upper pair of −κ. The dashed horizontal line meets the solid curve again at −κ − 1: the same l with the other j.
Live results
- κ
- -1
- UPPER PAIR l
- 0
- LOWER PAIR l′
- 1
- S⋅L ON UPPER PAIR
- 0.0 ħ²
Results follow this lesson’s model and assumptions. Displayed values are rounded.
Predict → change one variable → check
Plan a change before running it. Every other input stays at the saved baseline.
Saved baseline. Total angular momentum j: 0.5; Sign of κ: −1
This experiment is kept only while this page is open. It does not change saved course progress.
Catch the common trap
The tempting reading is that κ is shorthand for the pair (l, j), so that l is still a quantum number of the Dirac state and the sign of κ says whether the spin points up or down. Both halves are wrong. L² does not commute with H: the upper and lower pairs of every bound state carry different orbital labels, l and l′ = l ± 1, so even 1s₁/₂ has a p-wave small component and no single l describes the state. κ is the eigenvalue of an operator that is conserved, which l is not, and it is the same on both pairs only because β reverses the sign of σ⋅L + ħ on the lower one. Nor is the sign of κ a spin projection: mⱼ takes all 2j + 1 values for either sign. The sign records which branch, j = l + ½ or j = l − ½, the upper pair sits on, and with it the parity.
Practice & worked examples
3 authored examples. Make an attempt, then reveal the reasoning one step at a time.
EasyExample 1
List every state of the n = 3 shell of a hydrogen-like ion by κ, giving j, the orbital labels of the upper and lower pairs, the parity and the eigenvalue of K, and check that the shell holds 2n² states.
Sketch your answer or reasoning, then compare it with the authored solution. Your writing is not automatically graded or saved.
0 of 5 steps revealed.
- Quantum Mechanics II's n = nᵣ + l + 1 allows l = 0, 1 and 2. l = 0 gives only j = ½; l = 1 and l = 2 each give j = l ± ½, so there are five (l, j) pairs.
- Assign κ = −(l + 1) on the branch j = l + ½ and κ = +l on j = l − ½: 3s₁/₂ is −1, 3p₁/₂ is +1, 3p₃/₂ is −2, 3d₃/₂ is +2 and 3d₅/₂ is −3. κ = +3 would need l = 3, which n = 3 does not allow.
- The lower orbital label is l′ = 2j − l: 1, 0, 2, 1 and 3. The parity (−1)l is even, odd, odd, even, even, agreeing in each case with sgn(κ)(−1)κ.
- K = −κħ gives +ħ, −ħ, +2ħ, −2ħ and +3ħ. Check K² = J² + ħ²/4 on 3d₅/₂: j(j + 1) + ¼ = 35/4 + 1/4 = 9, so K² = 9ħ², as (3ħ)² requires. The largest eigenvalue is 3ħ = 3 × 1.0546 × 10⁻³⁴ J s = 3.16 × 10⁻³⁴ J s.
- Each κ holds 2j + 1 = 2|κ| values of mⱼ: 2 + 2 + 4 + 4 + 6 = 18 = 2 × 3², the count Quantum Mechanics II gives for n = 3.
Answer. κ = −1, +1, −2, +2, −3 for 3s₁/₂, 3p₁/₂, 3p₃/₂, 3d₃/₂, 3d₅/₂, with lower labels 1, 0, 2, 1, 3; 18 states in all; K runs from −2ħ to +3ħ = 3.16 × 10⁻³⁴ J s.
MediumExample 2
Use K on the upper pair to find S⋅L for hydrogen's 2p₁/₂ and 2p₃/₂ states. Then, with Unit 6's spin-orbit term and Quantum Mechanics II's ⟨r⁻³⟩, compute the 2P₃/₂–2P₁/₂ interval in GHz and compare it with the measured 10.969 GHz.
Sketch your answer or reasoning, then compare it with the authored solution. Your writing is not automatically graded or saved.
0 of 5 steps revealed.
- 2p₁/₂ has κ = +1 and 2p₃/₂ has κ = −2. Where β = +1, K = 2S⋅L/ħ + ħ = −κħ, so S⋅L = −(κ + 1)ħ²/2: −ħ² for 2p₁/₂ and +ħ²/2 for 2p₃/₂, a difference of 3ħ²/2.
- Unit 6's spin-orbit term, derived there with the Thomas factor and quoted here, is HSO = (1/2m²c²)(1/r)(dV/dr) S⋅L. Unit 6's kinetic correction depends only on n and l, so it shifts 2p₁/₂ and 2p₃/₂ equally, and its Darwin term vanishes for l = 1, so the interval is pure spin-orbit. For V = −αħc/r, (1/r)(dV/dr) = αħc/r³.
- Quantum Mechanics II gives ⟨r⁻³⟩ = 1/[n³l(l + ½)(l + 1)a₀³] = 1/(24a₀³) for n = 2 and l = 1, with a₀ = ħ/(mcα); quoted.
- ΔE = (αħc/2m²c²)(1/24a₀³)(3ħ²/2) = α⁴mc²/32. α is a pure number, so this is an energy. With α⁴mc² = 1.4490 × 10⁻³ eV, ΔE = 4.528 × 10⁻⁵ eV, and dividing by h = 4.1357 × 10⁻¹⁵ eV s gives 10.949 GHz.
- The measured interval, 10.969 GHz, is 0.18% higher. The reduced mass scales the result by μ/m = 0.99946, to 10.943 GHz, and the anomalous moment multiplies the spin-orbit term by g − 1 = 1 + 2a = 1.00232, giving 10.969 GHz; both corrections are quoted, the second from Unit 6.
Answer. S⋅L = −ħ² for 2p₁/₂ and +ħ²/2 for 2p₃/₂; ΔE = α⁴mc²/32 = 4.53 × 10⁻⁵ eV, so ΔE/h = 10.95 GHz, which becomes 10.969 GHz with the reduced mass and g − 2, matching the measured 10.969 GHz.
HardExample 3
Using K on the upper pair, write the Landé factor of one electron in a central field in terms of κ alone, for a spin g-factor gₛ. Evaluate it for κ = −1, +1 and −2 with gₛ = 2 and with gₛ = 2.0023193, compare with sodium's measured 3P₁/₂ and 3P₃/₂ values, 0.66581 and 1.33420, and give the mⱼ level spacing per tesla of each P level.
Sketch your answer or reasoning, then compare it with the authored solution. Your writing is not automatically graded or saved.
0 of 6 steps revealed.
- On the upper pair S⋅L = −(κ + 1)ħ²/2, so S⋅J = S⋅L + S² = −(κ + 1)ħ²/2 + 3ħ²/4 = (1 − 2κ)ħ²/4. From K² = J² + ħ²/4, J² = (κ² − ¼)ħ² = (2κ − 1)(2κ + 1)ħ²/4.
- Quantum Mechanics II's projection theorem, quoted, gives gⱼ = 1 + (gₛ − 1)⟨S⋅J⟩/⟨J²⟩ with gₗ = 1. The ratio is (1 − 2κ)/[(2κ − 1)(2κ + 1)] = −1/(2κ + 1), so gⱼ = 1 − (gₛ − 1)/(2κ + 1), one formula for both branches.
- Checks: gⱼ is dimensionless. κ = −1 gives gⱼ = gₛ, a pure spin, as an s state must. As |κ| grows gⱼ tends to 1, the orbital value. With gₛ = 2 it becomes gⱼ = 2κ/(2κ + 1).
- With gₛ = 2, κ = −1, +1 and −2 give 2, 2/3 = 0.6667 and 4/3 = 1.3333. With gₛ = 2.0023193 they give 2.0023, 4/3 − gₛ/3 = 0.66589 and 2/3 + gₛ/3 = 1.33411.
- Sodium's valence electron moves in a screened but central potential, so κ is good in the central-field model. The measured 0.66581(12) and 1.33420(20) agree with 0.66589 and 1.33411 within one standard uncertainty, while gₛ = 2 misses them by 0.13% and 0.065%.
- Adjacent mⱼ levels are gⱼμB B apart in energy, gⱼ(μB/h)B in frequency, with μB/h = 13.996 GHz T⁻¹: 0.66589 × 13.996 = 9.320 GHz T⁻¹ for 3P₁/₂ and 1.33411 × 13.996 = 18.672 GHz T⁻¹ for 3P₃/₂.
Answer. gⱼ = 1 − (gₛ − 1)/(2κ + 1). With gₛ = 2.0023193, 3P₁/₂ has 0.66589 and 3P₃/₂ has 1.33411 (measured 0.66581 and 1.33420), so their mⱼ spacings are 9.320 and 18.672 GHz T⁻¹.
Quick check
Select an answer and explain it before checking.
Review & continue
κ is the non-zero integer defined by Kψ = −κħψ, where K = β(Σ⋅L + ħ) is Dirac's conserved operator: |κ| = j + ½, and its sign says whether the upper component has l = j − ½ (κ < 0) or l = j + ½ (κ > 0).
- Explain the relationship without looking at the equation.
- Check a sign, a unit and a model assumption in your working.
- Return to the lab or worked example if a step is still unclear.