The Equilibrium Geometry, Harmonic Vibrational Frequencies, and Estimated ab Initio Limit for the Barrier to Planarity of the Ethylene Radical Cation

Abstract

The equilibrium geometry, barrier to planarity, and harmonic vibrational frequencies were determined theoretically for the ground state of the ethylene radical cation using several quantum mechanical methods and basis sets. The minimum-energy structure is a nonplanar D2 conformer separated from its symmetry equivalent by a planar transition state. The CCSD(T)/cc-pVTZ level of theory obtained an equilibrium C−C bond length and torsion angle of 1.4004 A and 21.0°, respectively, which are 0.005 A and 4.0° less than the experimentally derived values of Koppel et al. [J. Chem. Phys. 1978, 69, 4252]. The documented reliability of CCSD(T)/cc-pVTZ equilibrium geometries might call into question the experimentally derived geometry. In addition, the barrier to planarity was determined using a series of basis sets and methods aimed at reaching the complete-basis-set limit. The final vibrationless barrier was determined to be 116 ± 35 cm-1. Also, to aid in the interpretation of a recent infrared cavity-ring-down expe...