Usually the first step in describing the electronic wave function of a molecule or atom is to describe it with a single Slater determinant. I get that this is an independent particle approximation, and that in the context of Hartree-Fock, each electron moves in the average field of the other electrons. That's fine.
But when we correlate the electrons, this is done by generating excitations out of the Slater determinant, and then taking weighted combinations of them. For example, configuration interaction mixes the ground state Slater determinant with singly, doubly, triply, etc excited determinants. A fancier way of doing this is coupled cluster, where cluster operators generate excitations out of the Slater determinant.
Hermann Kummel says that we can think about electron correlation this way:
"The first thing one may imagine happening is that two particles mutually interact, thereby lifting themselves out of the Fermi sea, so that after the interaction both are in unoccupied orbitals"
Kümmel, Hermann. "Origins of the coupled cluster method." Theoretica chimica acta 80.2-3 (1991): 81-89.
Why can we (or should we) think about electron correlation that way?
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