Quantifying Electron Correlation of the Chemical Bond

J Phys Chem Lett. 2017 May 4;8(9):1937-1942. doi: 10.1021/acs.jpclett.7b00535. Epub 2017 Apr 17.

Abstract

The Interacting Quantum Atoms (IQA) method is used to analyze the correlated part of the Møller-Plesset (MP) perturbation theory two-particle density matrix. Such an analysis determines the effects of electron correlation within atoms and between atoms, which covers both bonds and nonbonded through-space atom-atom interactions within a molecule or molecular complex. Electron correlation lowers the energy of the atoms at either end of a bond, but for the bond itself, it can be stabilizing or destabilizing. Bonds are described in a two-dimensional world of exchange and charge transfer, where covalency is not the opposite of ionicity.