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Spin–Orbit Coupling

Spin–orbit coupling is an interaction between orbital angular momentum and spin. In its simplest central-potential form it has the angular structure

HSO=ξ(r) L⋅S,H_{\mathrm{SO}} = \xi(r)\,\mathbf L\cdot\mathbf S,

where ξ(r)\xi(r) is a scalar radial coefficient. The decisive algebraic point is that L⋅S\mathbf L\cdot\mathbf S is not diagonal in the separate Lz,SzL_z,S_z product basis, but it is diagonal in the coupled basis labeled by total angular momentum

J=L+S.\mathbf J=\mathbf L+\mathbf S.

This page is the canonical home for the angular-momentum-addition structure of spin–orbit coupling. How it fits into LS, jj, and intermediate coupling schemes is summarized in Angular Momentum Coupling Schemes. Spin–Orbit Coupling in Solids owns crystal-field projection, Rashba and Dresselhaus bands, spin Hall response, and the bridge to topological materials. Detailed atomic fine structure, relativistic derivations, and spectroscopy models belong to their respective canonical pages.

Spin–orbit coupling is time-reversal even when no fixed magnetic field is present: both L\mathbf L and S\mathbf S reverse. This is why spin–orbit coupling can reorganize levels without by itself destroying Kramers Degeneracy.

Begin with a spin-independent central Hamiltonian

H0=P22m+V(r).H_0 = \frac{\mathbf P^2}{2m} + V(r).

Its spatial eigenstates can be organized by orbital angular momentum ℓ\ell and magnetic quantum number mℓm_\ell. Including spin-1/21/2 without spin-dependent interactions simply adds a two-dimensional spin factor:

Hnℓspatial⊗C2.\mathcal H_{n\ell}^{\mathrm{spatial}} \otimes \mathbb C^2.

An uncoupled basis is

∣n,ℓ,mℓ⟩∣12,ms⟩,ms=±12.\lvert n,\ell,m_\ell\rangle \lvert \tfrac12,m_s\rangle, \qquad m_s=\pm\frac12.

This basis diagonalizes L2,Lz,S2,SzL^2,L_z,S^2,S_z. It is natural before orbital and spin angular momentum are coupled.

Once a spin–orbit term is present, the natural labels change. The Hamiltonian remains invariant under simultaneous rotations of the spatial and spin degrees of freedom, but it no longer treats the separate projections mℓm_\ell and msm_s as separately protected labels.

The scalar product

L⋅S=LxSx+LySy+LzSz\mathbf L\cdot\mathbf S = L_xS_x+L_yS_y+L_zS_z

is invariant under joint rotations generated by

J=L+S.\mathbf J=\mathbf L+\mathbf S.

Equivalently,

[Ji,L⋅S]=0,i=x,y,z.[J_i,\mathbf L\cdot\mathbf S]=0, \qquad i=x,y,z.

If ξ(r)\xi(r) is a radial scalar, then ξ(r)L⋅S\xi(r)\mathbf L\cdot\mathbf S is also rotationally invariant under the total angular momentum. Thus a central Hamiltonian with spin–orbit coupling satisfies

[H,Ji]=0,[H,J2]=0,[H,Jz]=0.[H,J_i]=0, \qquad [H,J^2]=0, \qquad [H,J_z]=0.

The conserved angular momentum is total angular momentum, not orbital angular momentum by itself. This is the same symmetry shift already previewed in Central Potentials and Rotational Symmetry.

For fixed ℓ\ell and spin s=1/2s=1/2, the coupled basis is

∣n,ℓ,s;j,mj⟩,s=12.\lvert n,\ell,s;j,m_j\rangle, \qquad s=\frac12.

It diagonalizes

L2,S2,J2,Jz.L^2,\quad S^2,\quad J^2,\quad J_z.

The allowed total angular momenta are

j=ℓ+12orj=ℓ−12,j = \ell+\frac12 \quad \text{or} \quad j = \ell-\frac12,

with the second option absent when ℓ=0\ell=0. For each jj,

mj=−j,−j+1,…,j.m_j=-j,-j+1,\ldots,j.

The coupled states are linear combinations of the uncoupled states with

mj=mℓ+ms.m_j=m_\ell+m_s.

The coefficients in that change of basis are Clebsch–Gordan coefficients. The important point for spin–orbit coupling is that one does not need every coefficient to obtain the energy splitting; the scalar identity below is enough.

From

J=L+S,\mathbf J=\mathbf L+\mathbf S,

one obtains

J2=L2+S2+2L⋅S.J^2 = L^2+S^2+2\mathbf L\cdot\mathbf S.

Therefore

L⋅S=12(J2−L2−S2).\mathbf L\cdot\mathbf S = \frac12 \left( J^2-L^2-S^2 \right).

On a coupled state,

J2∣n,ℓ,s;j,mj⟩=ℏ2j(j+1)∣n,ℓ,s;j,mj⟩,L2∣n,ℓ,s;j,mj⟩=ℏ2ℓ(ℓ+1)∣n,ℓ,s;j,mj⟩,S2∣n,ℓ,s;j,mj⟩=ℏ2s(s+1)∣n,ℓ,s;j,mj⟩.\begin{aligned} J^2\lvert n,\ell,s;j,m_j\rangle &= \hbar^2j(j+1)\lvert n,\ell,s;j,m_j\rangle, \\ L^2\lvert n,\ell,s;j,m_j\rangle &= \hbar^2\ell(\ell+1)\lvert n,\ell,s;j,m_j\rangle, \\ S^2\lvert n,\ell,s;j,m_j\rangle &= \hbar^2s(s+1)\lvert n,\ell,s;j,m_j\rangle. \end{aligned}

Thus

L⋅S⟶ℏ22[j(j+1)−ℓ(ℓ+1)−s(s+1)].\mathbf L\cdot\mathbf S \longrightarrow \frac{\hbar^2}{2} \left[ j(j+1)-\ell(\ell+1)-s(s+1) \right].

For spin-1/21/2, this becomes two possible eigenvalues:

L⋅S=ℏ2ℓ2forj=ℓ+12,\mathbf L\cdot\mathbf S = \frac{\hbar^2\ell}{2} \quad \text{for} \quad j=\ell+\frac12,

and

L⋅S=−ℏ2(ℓ+1)2forj=ℓ−12.\mathbf L\cdot\mathbf S = -\frac{\hbar^2(\ell+1)}{2} \quad \text{for} \quad j=\ell-\frac12.

For ℓ=0\ell=0, only j=1/2j=1/2 occurs and L⋅S=0\mathbf L\cdot\mathbf S=0.

If spin–orbit coupling is treated as a perturbation inside a fixed radial orbital sector, the angular part of the first-order shift is fixed by the preceding eigenvalue. Write the radial expectation value as

λnℓ=⟨ξ(r)⟩nℓ.\lambda_{n\ell} = \langle \xi(r)\rangle_{n\ell}.

Then

ΔEnℓj=λnℓℏ22[j(j+1)−ℓ(ℓ+1)−s(s+1)].\Delta E_{n\ell j} = \frac{\lambda_{n\ell}\hbar^2}{2} \left[ j(j+1)-\ell(\ell+1)-s(s+1) \right].

For s=1/2s=1/2,

ΔEj=ℓ+1/2=λnℓℏ2ℓ2,\Delta E_{j=\ell+1/2} = \frac{\lambda_{n\ell}\hbar^2\ell}{2},

while

ΔEj=ℓ−1/2=−λnℓℏ2(ℓ+1)2.\Delta E_{j=\ell-1/2} = -\frac{\lambda_{n\ell}\hbar^2(\ell+1)}{2}.

The splitting between the two jj multiplets is therefore

ΔEsplit=λnℓℏ22(2ℓ+1),\Delta E_{\mathrm{split}} = \frac{\lambda_{n\ell}\hbar^2}{2} \left( 2\ell+1 \right),

up to the sign convention and microscopic sign of λnℓ\lambda_{n\ell}.

Rotational symmetry still protects the mjm_j degeneracy: in the absence of external fields or other direction-selecting perturbations, the energy depends on n,ℓ,jn,\ell,j but not on mjm_j.

For a pp state, ℓ=1\ell=1 and s=1/2s=1/2. The allowed total angular momenta are

j=32andj=12.j=\frac32 \qquad \text{and} \qquad j=\frac12.

The coupled space decomposes as

ℓ=1⊗s=12⟶j=32⊕j=12.\ell=1 \quad\otimes\quad s=\frac12 \quad \longrightarrow \quad j=\frac32 \oplus j=\frac12.

The dimensions check:

(2ℓ+1)(2s+1)=3⋅2=6,(2\ell+1)(2s+1) = 3\cdot2 = 6,

and

(2⋅32+1)+(2⋅12+1)=4+2=6.(2\cdot\tfrac32+1) + (2\cdot\tfrac12+1) = 4+2 = 6.

The angular eigenvalues are

L⋅S=12ℏ2forj=32,\mathbf L\cdot\mathbf S = \frac12\hbar^2 \quad \text{for} \quad j=\frac32,

and

L⋅S=−ℏ2forj=12.\mathbf L\cdot\mathbf S = -\hbar^2 \quad \text{for} \quad j=\frac12.

Thus a spin–orbit interaction separates the six pp spin-orbital states into a fourfold j=3/2j=3/2 multiplet and a twofold j=1/2j=1/2 multiplet, before external fields or additional corrections are included. In symmetry language this is a case of degeneracy lifting with total rotational symmetry still intact.

In atomic central-field models, a common nonrelativistic correction has the schematic form

HSO=12m2c21rdVdr L⋅S,H_{\mathrm{SO}} = \frac{1}{2m^2c^2} \frac{1}{r} \frac{dV}{dr} \, \mathbf L\cdot\mathbf S,

when V(r)V(r) is the particle’s potential energy and the usual Thomas factor is included. Different effective Hamiltonians may use different masses, charges, signs, screening conventions, or solid-state parameters. This page does not derive the coefficient. It explains the universal angular algebra once the interaction has the form ξ(r)L⋅S\xi(r)\mathbf L\cdot\mathbf S.

For hydrogen, spin–orbit coupling is one part of fine structure. Relativistic kinetic-energy corrections and the Darwin term also contribute, and the full Dirac-Coulomb result organizes levels in a related but more complete way. The nonrelativistic Coulomb spectrum and its degeneracy are covered in Degeneracy of the Hydrogen Atom.

Spin–orbit coupling competes with magnetic-field coupling. In weak fields, atomic states are often first organized by the internal coupling into j,mjj,m_j levels, and the magnetic field then shifts those levels. This is the weak-field Zeeman regime.

In stronger fields, the magnetic interaction can compete with or dominate spin–orbit coupling. Then mℓm_\ell and msm_s can become more useful approximate labels than j,mjj,m_j. This crossover is the Paschen–Back regime discussed historically in Zeeman Effect Revisited.

The lesson is that “good quantum number” is a Hamiltonian statement. It depends on which terms are large enough to define the zeroth-order basis.

  • Treating mℓm_\ell and msm_s as separately conserved after a spin–orbit term has been turned on.
  • Forgetting that L2L^2 and S2S^2 remain good labels for the simple ξ(r)L⋅S\xi(r)\mathbf L\cdot\mathbf S central interaction.
  • Applying the spin–orbit splitting formula to ℓ=0\ell=0 states. When ℓ=0\ell=0, L=0\mathbf L=0 and this term vanishes.
  • Confusing the angular identity for L⋅S\mathbf L\cdot\mathbf S with a derivation of the microscopic coefficient ξ(r)\xi(r).
  • Assuming spin–orbit coupling removes all degeneracy. Rotational symmetry still protects degeneracy among mjm_j values.
  • Using one sign convention for HSOH_{\mathrm{SO}} while interpreting spectra from a source that defines the coefficient with the opposite sign.
  • J. J. Sakurai and J. Napolitano, Modern Quantum Mechanics, 3rd ed., Cambridge University Press, 2020.
  • R. Shankar, Principles of Quantum Mechanics, 2nd ed., Springer, 1994.
  • 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 Press, 1977.
  • H. A. Bethe and E. E. Salpeter, Quantum Mechanics of One- and Two-Electron Atoms, Springer, 1957.
  • C. J. Foot, Atomic Physics, Oxford University Press, 2005.
  1. Derive the eigenvalue of L⋅S\mathbf L\cdot\mathbf S for j=ℓ+1/2j=\ell+1/2.
Solution

Use

L⋅S=12(J2−L2−S2),\mathbf L\cdot\mathbf S = \frac12 \left( J^2-L^2-S^2 \right),

with s=1/2s=1/2 and j=ℓ+1/2j=\ell+1/2. Then

j(j+1)=(ℓ+12)(ℓ+32)=ℓ2+2ℓ+34.j(j+1) = \left( \ell+\frac12 \right) \left( \ell+\frac32 \right) = \ell^2+2\ell+\frac34.

Subtracting

ℓ(ℓ+1)+34=ℓ2+ℓ+34\ell(\ell+1)+\frac34 = \ell^2+\ell+\frac34

leaves ℓ\ell. Therefore

L⋅S=ℏ2ℓ2.\mathbf L\cdot\mathbf S = \frac{\hbar^2\ell}{2}.
  1. Show that an ss orbital has no spin–orbit splitting from ξ(r)L⋅S\xi(r)\mathbf L\cdot\mathbf S.
Solution

For an ss orbital, ℓ=0\ell=0. The orbital angular momentum operator vanishes on the ℓ=0\ell=0 subspace:

L2=0.L^2=0.

The only allowed total angular momentum is j=1/2j=1/2. The identity gives

ℏ22[12(12+1)−0−12(12+1)]=0.\frac{\hbar^2}{2} \left[ \frac12\left(\frac12+1\right) -0 -\frac12\left(\frac12+1\right) \right] =0.

Thus L⋅S\mathbf L\cdot\mathbf S has eigenvalue zero, so this spin–orbit term gives no ss-state splitting.

  1. Count the states for ℓ=2\ell=2 and s=1/2s=1/2 after spin–orbit coupling organizes them by jj.
Solution

Before coupling, the product space has dimension

(2ℓ+1)(2s+1)=5⋅2=10.(2\ell+1)(2s+1) = 5\cdot2 = 10.

The allowed total angular momenta are

j=52andj=32.j=\frac52 \qquad \text{and} \qquad j=\frac32.

Their dimensions are

2⋅52+1=6,2⋅32+1=4.2\cdot\frac52+1=6, \qquad 2\cdot\frac32+1=4.

The total is 6+4=106+4=10, matching the uncoupled dimension.

  1. Explain why spin–orbit coupling preserves mjm_j degeneracy but can split states with different jj.
Solution

The interaction ξ(r)L⋅S\xi(r)\mathbf L\cdot\mathbf S is a scalar under joint rotations generated by J\mathbf J. Therefore the Hamiltonian commutes with JiJ_i, J2J^2, and JzJ_z. Rotational symmetry prevents different mjm_j values inside the same jj multiplet from having different energies.

However, the eigenvalue of L⋅S\mathbf L\cdot\mathbf S depends on jj through

ℏ22[j(j+1)−ℓ(ℓ+1)−s(s+1)].\frac{\hbar^2}{2} \left[ j(j+1)-\ell(\ell+1)-s(s+1) \right].

Thus different jj multiplets can have different spin–orbit shifts while the mjm_j states inside each multiplet remain degenerate.