Ab initio study of the barriers to methyl torsion and torsional frequencies of acetyl molecules

A wide range of ab initio and hybrid density functional methods and basis sets have been employed to calculate the barriers to methyl internal rotation in a range of molecules with the acetyl moiety. Comparison is made of the computed torsional frequency with the experimental torsional frequency, νobs, for each molecule. With the MP2/6-311+G(3df,2p) combination of method and basis set, the agreement is better than 4 cm−1 for most of the molecules, where νobs or the V3 barrier is well-determined experimentally.