Relativistic Correction for

Hydrogen-Fine Structure
● Bohr attempted to explain spectra of hydrogen and hydrogen like atoms using his
postulates and derived a non-relativistic equation given as,

● Sommerfeld was the first to attempt and explain the observed fine-structure of
hydrogen spectral lines by introducing the relativistic variation of mass of the electron
moving in elliptic orbits.
● A more perfect account of observed fine-structure is, however given by quantum
mechanics taking spin-orbit interaction as well as relativity correction into account.
● 1. Spin-Orbit Interaction
● The spin-orbit interaction is an interaction between an electron’s spin magnetic dipole
moment and internal magnetic field of an atom which arises from the orbital motion of
the electron through the nuclear electric field .
● Though being a relatively weak interaction it is partly responsible for fine-structure of
the excited states of one-electron atoms.
● Let the electric field be a gradient of a potential V(r); where r is electron-nuclei
distance,

● The magnetic field in a reference frame fixed with the electron arising from the orbital
motion of the electron with velocity in the electric field is given by,
● Finding the expression for the magnetic potential energy of orientation is,

● This is enegry in reference frame of system in which electron is at rest, on rellativstic

transformation to normal frame of reference for nucleus at rest is,

● We express this quantity in terms of l,s and j

● In general , is not constant during the electron motion, Hence we must take its
average value over the unperturbed motion. Also the potential for hydrogen like atoms
is inverse square coulomb potential so the above expression takes the form of
● The average value of is evaluated by using a generating function representation
for the hydrogen radial eigenfunctions

● The magnetic potential energy the becomes,

● Where is rydberg constant for an infinitely heavy nucleus, and is fine structure
constant.
● The term-shift due to spin orbit interaction is

● For hydrogen like atoms and so and terms shifts corresponding to

and are

● Thus, the spin-orbit interaction causes each term of a given l to split into two terms of
different j’s, one dispalced upwards and the other downwards. The difference
between them is

● Thus, the spin-orbit interaction splitting increases with increasing atomic number and
is smaller for higher n and higher l. It is zero for S-terms.
● 2. Quantum Mechanical Relativity Correction