Benchmark calculations for bond dissociation energies and enthalpy of formation of chlorinated and brominated polycyclic aromatic hydrocarbons. Issue 47 (6th September 2021) - Xu, Shenying
Abstract : Benchmark calculations using state-of-the-art DFT functionals and composite methods for bond dissociation energy and enthalpy of formation of halogenated polycyclic aromatic hydrocarbons are performed. Abstract : Thermodynamic properties, i.e., bond dissociation energies and enthalpy of formation, of chlorinated and brominated polycyclic aromatic hydrocarbons play a fundamental role in understanding their formation mechanisms and reactivity. Computational electronic structure calculations routinely used to predict thermodynamic properties of various species are limited for these compounds due to large computational cost to obtain accurate results by employing high-level wave function theory methods. In this work, a number of composite model chemistry methods (CBS-QB3, G3MP2, G3, and G4) are used to compute bond dissociation energies and enthalpies of formation of small to medium-size chlorinated and brominated polycyclic aromatic hydrocarbon compounds. The enthalpy of formation is derived via the atomization method and compared against the recommended values. Statistical analysis indicates that G4 is the best method. For comparison, three commonly used density functional theory (DFT) methods (M06-2X, ωB97X-D and B2PLYP-D3) with various basis sets including 6-311++G(d, p), cc-pVTZ, and cc-pVQZ in the prediction of bond dissociation energies and enthalpies of formation have been tested using the optimized geometries at the same M06-2X/6-311++G(d, p) level of theory. It is found that ωB97X-D/6-311++G(d, p) shows the best performance in computing the bond dissociation energies, while ωB97X-D/cc-pVTZ exhibits the best prediction in enthalpy of formation of the studied reaction systems. The structural effect on the bond dissociation energies and enthalpy of formation of chlorinated and brominated polycyclic aromatic hydrocarbons are then systematically analyzed. Based on comparisons of the various methods, reliable DFT methods are recommended for future theoretical studies on large chlorinated and brominated polycyclic aromatic hydrocarbons considering both accuracy and computational cost. This work, to the authors' knowledge, is the first to systematically benchmark theoretical methods for the accurate prediction of thermodynamic properties for chlorinated and brominated polycyclic aromatic hydrocarbons.