Ring Conserved Isodesmic Reactions: A New Method for Estimating the Heats of Formation of Aromatics and PAHs

Abstract

Density functional theory (DFT) has been used along with isodesmic reaction schemes to estimate heats of formation for aromatics and polynuclear aromatic hydrocarbons (PAHs). Calculations have been performed for 42 molecules, 12 of which have uncertain or unknown experimental values, using the B3-LYP functional with the small 6-31G(d) basis set. Heats of formation for the group of test molecules were estimated using both conventional bond separation (BS) isodesmic reactions as well as a new technique of ring conserved (RC) isodesmic reactions which is able to correct systematic errors in B3-LYP calculations. When a ring conserved isodesmic reaction based on delocalization energies is used, the estimated heat of formation is more accurate than that obtained by the bond separation technique. The methodology for creating and using appropriate ring conserved isodesmic reactions is discussed. The present scheme also compares favorably against a recently developed bond centered group additivity scheme that was tested against a large number of PAH molecules.