The geometry and forcefield of acetylene

Abstract

The variational method has been used to determine the geometry and ground state potential surface of acetylene. All the parameters were refined through a least-squares fit to J = 0, 1 levels for C2H2 and C2D2. A new program was written to evaluate the rovibrational energy levels; in particular, primitive basis sets were developed for all values of J taking into account the singularity for linear geometries. Thus Σ, II, δ states can be refined. The full theory for tetraatomic linear molecules is presented. In this refinement 150 observed levels were used as data, below 10 000cm−1. The geometry was refined and gives Re(CC) = 1.2028 Å, Re(CH) = 1.0618 Å, to be compared with the best experimentally derived values of 1.2027 ± 0.0005 Å, 1.062 ± 0.001 Å, respectively. The zero point energies are 5771.1cm−1 for C2H2 and 4571.1cm−1 for C2D2.