Many-electron Systems and the Pauli Principle

It is shown how the quantum Hamiltonian for a general molecule is set up, using the ‘quantum recipe’ of chapter 3. In the most restrictive Born Oppenheimer approximation, the nuclei are held fixed and the Schrodinger equation (SE) is set up for the electrons only. The wavefunction depends on the positions and spin projections of all electrons. The electron spin projection is introduced heuristically as another two-valued electron degree of freedom. The electronic SE cannot be solved exactly, and (spin-) orbitals are introduced to construct an approximate wavefunction. The Pauli principle demands that a many-electron wavefunction is antisymmetric upon the exchange of electron labels, which leads to the construction of the approximate orbital-model wavefunction as a Slater determinant rather than a simple Hartree product. The orbital model wavefunction does not describe the Coulomb electron correlation, but it incorporates the (Fermi) correlation leading to the Pauli exclusion.