Application of the correlation consistent composite approach (ccCA) to third-row (Ga-Kr) molecules


The correlation consistent composite approach (ccCA) has been applied to the G3/05 training set of 51 energetic properties for the atoms and molecules that contain the 4p elements, Ga-Kr. When atomic and molecular first-order spin orbit coupling corrections are added to open shell atoms and molecules, the ccCA has a mean absolute deviation from experiment (MAD) of 0.95 kcal mol -1, an improvement of 0.10 kcal mol-1 over G3 and G3X model chemistries. The performance of the ccCA on third-row-containing atoms and molecules Is, therefore, commensurate in accuracy with previous studies on lighter main group elements H-Ar. While the typical methods used to compute theoretical molecular spin orbit corrections may go against the spirit of "black box" model chemistries, such corrections may be necessary for molecules containing heavy elements such as Ga-Kr. For example, when second-order spin orbit corrections are added to the atomic and molecular energies, the ccCA MAD Is reduced to 0.88 kcal mol-1. © 2008 American Chemical Society.

Publication Title

Journal of Chemical Theory and Computation