Electron Correlation: Nature's Weird and Wonderful Chemical Glue. Issue 1 (20th December 2021)

• Record Type: Journal Article
• Authors: Martin, Jan M. L.
• Other Names: Gershoni-Poranne Renana guestEditor.; Keinan Ehud guestEditor.; Kozuch Sebastian guestEditor.
• Is Part Of: Israel journal of chemistry. Volume 62:Issue 1/2(2022)
• Page Start: n/a
• Page End: n/a
• Publication Date: 2021-12-20
• Subjects: electron correlation -- chemical bonding -- intermolecular interactions -- wavefunction ab initio -- density functional theory; Chemistry -- Periodicals; 540.5
• DOI: 10.1002/ijch.202100111
• Languages: English
• ISSNs: 0021-2148

Abstract

Abstract: 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 2 nd 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". Abstract :