Electron Correlation: Nature's Weird and Wonderful Chemical Glue

It can be argued that electron correlation, as a concept, deserves the same prominence in general chemistry as molecular orbital theory. We show how it acts as Nature's “chemical glue” at both the molecular and supramolecular levels. Electron correlation can be presented in a general chemistry course in an at least somewhat intuitive manner. We also propose a simple classification of correlation effects based on their length scales and the size of the orbital gap (relative to the two-electron integrals). In the discussion, we also show how DFT can shed light on wavefunction theory, and conversely. We discuss two types of “honorary valence orbitals”, one related to small core-valence gaps, the other to the ability of empty 3d orbitals in 2nd row elements to act as backbonding acceptors. Finally, we show why the pursuit of absolute total energies for their own sake becomes a sterile exercise, and why atomization energies are a more realistic “fix point”.