Dynamical electron correlation and the chemical bond. III. Covalent bonds in the A 2 molecules (A = C-F)

• Published in: Physical chemistry chemical physics : PCCP Vol. 26; no. 38; pp. 24809 - 24820
• Main Authors: Dunning, Jr, Thom H, Xu, Lu T
• Format: Journal Article
• Language: English
• Published: England Royal Society of Chemistry (RSC) 02.10.2024
• ISSN: 1463-9076; 1463-9084
• DOI: 10.1039/D4CP01695E

For most molecules the spin-coupled generalized valence bond (SCGVB) wavefunction accounts for the effects of non-dynamical electron correlation. The remaining errors in the prediction of molecular properties and the outcomes of molecular processes are then solely due to dynamical electron correlation. In this article we extend our previous studies of the effects of dynamical electron correlation on the potential energy curves and spectroscopic constants of the AH and AF (A = B-F) molecules to the homonuclear diatomic molecules, A (A = C-F). At large the magnitude of Δ ( ), the correlation energy of the molecule relative to that in the atoms, increases nearly exponentially with decreasing , just as we found in the AH and AF molecules. But, as continues to decrease the rate of increase in the magnitude of Δ ( ) slows, eventually leading to a minimum for C -O . Examination of the SCGVB wavefunction for the N molecule around the minimum in Δ ( ) did not reveal a clear cause for this puzzling behavior. As before, the changes in Δ ( ) around were found to have an uneven effect on the spectroscopic constants of the A molecules.