Improved virtual orbital multireference Møller–Plesset study of the ground and excited electronic states of protonated acetylene, C2H

Abstract

The ground state geometries and associated normal mode frequencies of the classical and nonclassical protonated acetylene ion, i.e., the vinyl cation C2H, are computed using the complete active space self-consistent field and improved virtual orbital (IVO) complete active space configuration interaction methods. In addition, the minimum-energy reaction path for the classical to nonclassical interconversion is determined (as are excitation energies) using the IVO modification of multireference Møller–Plesset (MRMP) perturbation theory. The IVO-MRMP treatment predicts the nonclassical structure to be 4.8 kcal/mol more stable than the classical one, which is consistent with other high level theoretical estimates. The proton affinity of acetylene from the IVO-MRMP treatment (154.8 kcal/mol) also agrees well with experiment (153.3 kcal/mol) and with earlier CASPT2 calculations (154.8 kcal/mol). We further report geometries and vibrational frequencies of low lying excited states of C2H, which have not been observed and/or studied before. Comparisons with previous highly correlated calculations further demonstrate the computational efficiency of the IVO-MRPT methods