Past exam of the chemistry A course of the University of Cambridge / 2022 / Paper 1 / A2 / a

The Pauli exclusion principle requires the complete electron wavefunction to change sign on exchange of any two electrons, including both position and spin labels. Let $a=1s$ and $b=2s$ be normalized, orthogonal spatial atomic orbitals, and let $\alpha ,\beta$ denote spin up and down.

The symmetric and antisymmetric spatial functions areThe singlet state isThe three triplet states share the antisymmetric spatial factor:Every factor and complete product is normalized. Here the subscripts are $(S,M_S)$; the spatial electron configuration is $1s2s$ in each case.

Let $P_{12}$ exchange the complete labels of the two electrons. The spatial factors obey $P_{12}{\Phi }_{\pm }=\pm {\Phi }_{\pm }$. The singlet state spin factor is antisymmetric, while each triplet state spin factor is symmetric. Thus in all four casesas required by the Pauli exclusion principle. In particular, the $M_S=0$ triplet state remains a triplet despite having opposite measured spin projections in each product term.

For a spin-independent Hamiltonian and the same fixed spatial atomic orbitals, direct evaluation giveswhere $J_{ab}$ is the direct Coulomb integral and $K_{ab}>0$ is the exchange integral for the helium $1s,2s$ pair. ThereforeThe antisymmetric spatial wavefunction vanishes when the two positions coincide and reduces their Coulomb repulsion. The lower energy of the maximum-spin member of this fixed electron configuration is the first of Hund's rules.