ABINITIO SCF-MO CALCULATIONS OF THE POTENTIAL SURFACES OF THIOCARBONYLS .2. H2CS, HFCS, CLFCS, AND CL2CS

Potential energy surfaces and equilibrium geometries for the ground and first excited triplet states of H2CS, HFCS, ClFCS, and Cl 2CS have been calculated using ab initio SCF MO methods. The triplet state out-of-plane bending mode frequencies have been calculated using a perturbation theoretical treatment and a suitable analytic approximation to the potential along the out-of-plane bending coordinate. Where experimental results are available, good agreement exists between calculated and experimental data. The equilibrium out-of-plane angle in the lowest triplet state is correlated with the decrease in the p electron density on the carbon atom accompanying the change from the planar to the equilibrium out-of-plane conformation. © 1979 American Institute of Physics.