Dynamical electron correlation and the chemical bond. I. Covalent bonds in AH and AF (A = B-F).

Abstract

Dynamical electron correlation has a major impact on the computed values of molecular properties and the energetics of molecular processes. This study focused on the effect of dynamical electron correlation on the spectroscopic constants (Re, ωe, De), and potential energy curves, ΔE(R), of the covalently bound AH and AF molecules, A = B-F. The changes in the spectroscopic constants (ΔRe, Δωe, ΔDe) caused by dynamical correlation are erratic and, at times, even surprising. These changes can be understood based on the dependence of the dynamical electron correlation energies of the AH and AF molecules as a function of the bond distance, i.e., ΔEDEC(R). At large R, the magnitude of ΔEDEC(R) increases nearly exponentially with decreasing R, but this increase slows as R continues to decrease and, in many cases, even reverses at very short R. The changes in ΔEDEC(R) in the region around Re were as unexpected as they were surprising, e.g., distinct minima and maxima were found in the curves of ΔEDEC(R) for the most polar molecules. The variations in ΔEDEC(R) for R ≲ Re are directly correlated with major changes in the electronic structure of the molecules as revealed by a detailed analysis of the spin-coupled generalized valence bond wave function. The results reported here indicate that we have much to learn about the nature of dynamical electron correlation and its effect on chemical bonds and molecular properties and processes.