Ab-initio study of the molecules bc and b2c

Abstract

The potential energy surface for the B2C molecule and the potential energy curve for the ground state of BC have been investigated using full-valence complete active space SCF (CASSCF), augmented coupled cluster [CCSD(T)] and multireference treatments. The ground state of B2C is an extraordinarily stable ring (Sigma D-e=261.6+/-1 kcal/mol) with two 2-electron pi systems. The first excited state is linear BCB (1 Sigma(g)(+)), which is essentially biconfigurational due to a (4 sigma(g))-(3 sigma(u)) near degeneracy. Anharmonic spectroscopic constants were obtained from quartic force fields at the CCSD(T) level with a correlation-consistent basis set of [4s3p2dlf] quality. A severe Fermi resonance exists between the bending and symmetric stretching modes. All computed intensities are fairly weak. Spectroscopic constants for BC using elaborate multireference techniques were very well reproduced using the CCSD(T) method with a spin-restricted Hartree-Fock reference configuration, but not with an unrestricted Hartree-Fock reference. This suggests that even moderate levels of spin contamination that do not significantly affect relative energies may have a detrimental effect on computed spectroscopic constants.