The Chemical Bond in C2

Abstract

Quantum chemical calculations using the complete active space of the valence orbitals have been carried out for Hn CCHn (n=0-3) and N2. The quadratic force constants and the stretching potentials of Hn CCHn have been calculated at the CASSCF/cc-pVTZ level. The bond dissociation energies of the C-C bonds of C2 and HC≡CH were computed using explicitly correlated CASPT2-F12/cc-pVTZ-F12 wave functions. The bond dissociation energies and the force constants suggest that C2 has a weaker C-C bond than acetylene. The analysis of the CASSCF wavefunctions in conjunction with the effective bond orders of the multiple bonds shows that there are four bonding components in C2, while there are only three in acetylene and in N2. The bonding components in C2 consist of two weakly bonding σ bonds and two electron-sharing π bonds. The bonding situation in C2 can be described with the σ bonds in Be2 that are enforced by two π bonds. There is no single Lewis structure that adequately depicts the bonding situation in C2. The assignment of quadruple bonding in C2 is misleading, because the bond is weaker than the triple bond in HC≡CH.

Keywords: bond order; bond strength; bonding analysis; carbon; force constants; multiple bonding.