Ethynylvinylidene

Abstract

AbstractEthynylvinylidene, an energetically low‐lying isomer of diacetylene, has been studied using ab initio molecular electronic structure theory. Geometries of diacetylene, ethynylvinylidene, and the transition state between them have been optimized using the double‐ζ plus polarization (DZP) and triple‐ζ plus double polarization function (TZ2P) basis sets with the self‐consistent field (SCF), configuration interaction with single and double excitations (CISD), coupled cluster with single and double substitutions (CCSD), and CCSD with perturbatively included connected triple substitutions [CCSD(T)] methods. At the TZ2P CCSD(T) level of theory only single point energies have been determined at the TZ2P CCSD geometries. Harmonic vibrational frequencies and infrared (IR) intensities are reported for the three stationary points at the DZP SCF, TZ2P SCF, and DZP CISD levels of theory. For ethynylvinylidene, rotational constants, dipole moments, and dipole moment components along the principal axes are also given. This isomer is found to be an extremely shallow minimum on the C4H2 potential energy surface, and the classical barrier to rearrangement (to diacetylene) is vanishingly small at the highest level of theory.