9.7: Helium
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Helium is the simplest system for which we are unable to accurately calculate the energy.
For a single electron moving in the field of a helium nucleus, the spatial wavefunctions are similar to those of hydrogen |unlm⟩.
When a second electron is added, a reasonable basis set is exchange-symmetrised wavefunctions consisting of spin states multiplying hydrogenic spatial parts:
(unlm(r1)un′l′m′(r2)±un′l′m′(r1)unlm(r2))
Since the overall wavefunction must be antisymmetric, the singlet (exchange-antisymmetric) spin states must combine with symmetric spatial states, and the triplet (exchange-symmetric) spin states must combine with antisymmetric spatial states.
If both electrons were in the same spatial state, the antisymmetric spatial wavefunction would be:
|(a(r1)a(r2)−a(r2)a(r1))⟩=0
Hence there is no triplet for the ground state.