The accurate CH/π interaction energy of the benzene-methane model system was experimentally and theoretically determined. In the experiment, mass analyzed threshold ionization spectroscopy was applied to the benzene-methane cluster in the gas phase, prepared in a supersonic molecular beam. The binding energy in the neutral ground state of the cluster, which is regarded as the CH/π interaction energy for this model system, was evaluated from the dissociation threshold measurements of the cluster cation. The experimentally determined binding energy (D0) was 1.03-1.13 kcal/mol. The interaction energy of the model system was calculated by ab initio molecular orbital methods. The estimated CCSD(T) interaction energy at the basis set limit (De) was -1.43 kcal/mol. The calculated binding energy (D0) after the vibrational zero-point energy correction (1.13 kcal/mol) agrees well with the experimental value. The effects of basis set and electron correlation correction procedure on the calculated CH/π interaction energy were evaluated. Accuracy of the calculated interaction energies by DFT methods using BLYP, B3LYP, PW91 and PBE functionals was also discussed.
ASJC Scopus subject areas
- Physical and Theoretical Chemistry