Theoretical Thermochemistry for Organic Molecules: Development of the Generalized Connectivity-Based Hierarchy.

Abstract

A generalized, unique thermochemical hierarchy applicable for all closed shell organic molecules is developed in this paper. In this chemically intuitive, structure-based approach, the connectivity of the atoms in an organic molecule is used to construct our hierarchy called "connectivity-based hierarchy" (CBH). The hierarchy has several rungs and ascending up the hierarchy increasingly balances the reaction energy. It requires no prior knowledge of the types of molecules and hybridizations for the appropriate balancing of the bond types and the bonding environments of the atoms. The rungs can be generated by an automated computer program for any closed shell organic molecule, and the first three rungs generate the simplest reactions for the widely used isodesmic, hypohomodesmotic, and hyperhomodesmotic schemes. The generated reaction schemes are unique for each rung and are derived in a simpler manner than previous approaches, avoiding potential errors. This work also suggests that for closed shell organic molecules, the previously well-studied homodesmotic scheme does not have a fundamental structure-based origin. In a preliminary application of CBH, density functional theory has been used to calculate accurate enthalpies of formation for a test set of 20 organic molecules. The performance of the hierarchy suggests that it will be useful to predict accurate thermodynamic properties of larger organic molecules.