For a point, stationary proton, the leading hydrogen fine structure comes from three order- contributions to the nonrelativistic electron Hamiltonian:
These are the relativistic kinetic-energy correction, spin-orbit interaction and Darwin term. The spin-orbit coefficient includes the Thomas precession factor of one half; . The Coulomb Darwin contribution is a positive contact term, relevant for S states. These corrections distinguish total angular momentum , while leaving magnetic substates degenerate without an external field.
Writing , the combined hydrogen fine-structure correction is
Thus the splitting is of order times the principal binding energy. In the shell, and remain degenerate in this approximation, while is higher by . The Lamb shift lifts the remaining S–P degeneracy; hyperfine structure is a separate nuclear-spin effect. Neither is part of the displayed correction. Nuclear recoil and finite nuclear size have also been neglected. [ref]
Figure 1.
Leading hydrogen n=2 fine-structure corrections retain the 2S1/2–2P1/2 degeneracy
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