An accurate ab initio quartic force field and vibrational frequencies for cyclopropenylidene

Abstract

The singles and doubles coupled-cluster method that includes a perturbative correction for connected triple excitations, denoted CCSD(T), is used in conjunction with an spdf quality one-particle basis set to determine an accurate quartic force field for cyclopropenylidene. A second-order perturbation theory treatment of vibrational anharmonicities, together with proper treatment of Fermi resonances, is used to predict fundamental vibrational frequencies of cyclopropenylidene and its 13C and deuterium isotopomers. Agreement between theory and the available experimental data is excellent. It is demonstrated that four vibrational bands assigned to cyclopropenylidene in 1984 matrix isolation experiments are correct, contrary to a recent suggestion. The anharmonic progression in the C-H stretches is examined and found to be similar for both the symmetric and antisymmetric C-H stretches, contrary to the findings from another recent study.