Carbene Proton Attachment Energies: Theoretical Study

Abstract

The geometries and electronic energies of six singlet carbenes, with methyl and phenyl substituents, and the corresponding carbenium ions were obtained using several density functional theory (DFT) variants and the second-order Møller-Plesset method for electron correlation and compared with G3 results, with the aim to determine a relatively low-cost computational protocol that is sufficiently accurate for the specific molecules and ions of interest. Some additional calculations were performed at the CCSD(T) level. Results for diphenylcarbene, methylphenylcarbene, and their cations, which were not previously investigated by ab initio methods, are reported as are calculations on methylene, methylcarbene, dimethylcarbene, and phenylcarbene. The MPW3LYP/6-311+G(d,p) hybrid DFT level was found to give results that were in close agreement with those obtained using G3 theory, with a mean absolute deviation (MAD) of 1.76 kcal/mol for the calculated proton attachment energies (PAEs). Equilibrium geometries obtained with this method were compared with those obtained at the MP2/6-311G(d,p) level of theory, and bond lengths and bond angles had MADs of 0.005 A and 1.0 degrees, respectively. Harmonic vibrational frequencies of all the carbene molecules and the corresponding ions were computed to verify that the stationary points were true minima, to obtain zero-point corrected energies, to assist in infrared studies of the molecules. The recommended combination of method and basis set is expected to be a useful framework that uses modest amounts of computer resources to obtain usable thermochemical data on moderate-sized hydrocarbons and hydrocarbon cations, including coal-mimetic species.