jp8b03321_si_001.pdf (646.46 kB)

Download file# Gas-Phase Heat of Formation Values for Buckminsterfullerene (C_{60}), C70 Fullerene (C_{70}), Corannulene, Coronene, Sumanene,
and Other Polycyclic Aromatic Hydrocarbons Calculated Using Density
Functional Theory (M06 2X) Coupled with a Versatile Inexpensive Group-Equivalent
Approach

journal contribution

posted on 02.08.2018, 17:40 by John A. BumpusA straightforward procedure using
density functional theory (M06
2X) coupled with a group-equivalent approach is described that was
used to calculate gas-phase heat of formation (Δ

_{f}*H*°_{g,298}) values for buckminsterfullerene (C_{60}), C70 fullerene (C_{70}), corannulene, coronene, and sumanene. This procedure was also used to calculate exceptionally accurate Δ_{f}*H*°_{g,298}values for a variety of single-ring aromatic and 2–7 ring polycyclic aromatic hydrocarbons (PAHs) as well as a large selection of other hydrocarbons and phenols. The approach described herein is internally consistent, and results for C_{60}, C_{70}, corannulene, coronene, and sumanene are in very close agreement with results reported by others who used higher-level computational theory. Statistical analysis of a test set containing benzene and 18 two to seven ring PAHs demonstrated that by using this approach a mean absolute deviation (MAD) and a root-mean-square deviation (RMSD) of 0.8 and 1.3 kJ/mol, respectively, were achieved for reference/experimental Δ_{f}*H*°_{g,298}values versus calculated/predicted Δ_{f}*H*°_{g,298}values. For statistical analysis of a larger test set containing 235 aromatic and aliphatic hydrocarbons and phenols, a MAD and a RMSD of 1.2 and 1.9 kJ/mol, respectively, were achieved for reference/experimental Δ_{f}*H*°_{g,298}values versus calculated/predicted Δ_{f}*H*°_{g,298}values.