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Chapter 4. Atomic Spectroscopy
Hartree Approximation (mean field approximation) - electronelectron repulsion is replaced with average mean field potential.
Many electron system is described in terms of hydrogen-like single
electron states.
n : principal quantum number (shell)
l, m, s : angular momentum, magnetic momentum (z-component of l),
and spin quantum numbers of a single electron
Orbital: specified by n and l
Configuration - Assignment of electrons to orbitals
L, M, S : quantum numbers for sum over all the electrons
Term Symbol:
L= 0 S
1 P
2 D
3 F
J: Quantum number for
sum of L and S
4 G
Possible combinations of angular momenta and term symbols for two
equivalent p electrons.
Hund’s rules
(i) Of the terms arising from equivalent electrons, those with the
highest multiplicity lie the lowest in energy.
(ii) Of these, the lowest is that with the highest value of L.
Lande’s interval rule
For less than half-filled orbitals, smaller J has lower energy.
For more than half-filled orbitals, larger J has lower energy.
Selection rules
Laporte’s Rule
This is due to the fact that the transition dipole vector has odd
inversion symmetry and that the sum of li dtermines the
inversion symmetry of the eigenstate.
Examples of Atomic Spectra
1. Alkali metal atoms (Li,Na, K, Rb, Cs) - (Closed shell)ns1
Emission has at least three series in the visible region.
is forbidden because of
Laporte’s rule)
The principal series in the sodium atom (Na)
n=3: Sodium D lines: 589.592 nm, 588.995 nm
Hydrogen atom
Ground state (
Excited states (
Helium atom
Ground state configuration:
Ground state term:
Excited state configurations:
Excited state terms: