Journal of Chemical Physics, Vol.101, No.1, 430-435, 1994
Equilibrium Geometry of Isocyanomethylene (Hcnc) and Comparison to the Troublesome Isomer Cyanomethylene (Hccn)
Inspired by the recent experimental study of the radical anions HCCN- and HCNC- and by earlier examinations of HCCN, the equilibrium geometry of the HCNC molecule has been investigated using both self-consistent field (SCF) and configuration interaction methods including single and double excitations (CISD). The largest basis set used was a triple-zeta plus double polarization with diffuse functions and higher angular momentum functions appended to each atom [TZ2P(f,d)+diff]. Using this basis, the H-C-N equilibrium angle is predicted to be 128.5 degrees at the CISD level of theory. Additionally, the zero point vibrational energy (ZPVE) corrected energy separation of the bent and linear conformations was predicted to be 10.1 kcal mol(-1) at the CISD level of theory with the largest basis set employed. The barrier to linearity is 7.7 kcal mol(-1) at the CCSD level of theory and 6.9 kcal mol(-1) at the CCSD(T) level of theory, employing the CISD optimized geometries with a basis that was comprised of triple-zeta plus double polarization with higher angular momentum functions appended to each atom [TZ2P(f,d)]. These results were compared to those obtained in previous ab initio investigations of HCCN, which has been dubbed a quasilinear molecule by the most recent experimental investigators. HCNC is predicted to lie 22.2 kcal mol(-1) above HCCN at the CISD level of theory, with a the TZ2P(f,d) basis. The differences between the two isomers are discussed and HCNC is predicted to be a definitively bent molecule, rather than quasilinear.
Keywords:GAUSSIAN BASIS FUNCTIONS;RESTRICTED HARTREE-FOCK;SHELL COUPLED CLUSTER;ATOMIC BASIS SETS;FIRST-ROW ATOMS;TRIPLE EXCITATIONS;CARBANION SPECTROSCOPY;MOLECULAR CALCULATIONS;GROUND-STATE;CONTRACTION