Abstract
Ab initio molecular orbital calculations including electron correlation effects within a number of different basis sets have been used to study the geometries and energies of phenylsilanitrile/isonitrile isomers. The CH
3SiN/CH
3NSi isomers have also been studied. In contrast to the carbon analogues, the silaisonitrile is more stable than the silanitrile by about 50 kcal mol
−1 at the correlated level of theory. The SiN bond length is found to be of similar magnitude in both the methyl and phenyl derivatives and is considerably shorter than any known SiN single or double bonds. The molecule PhNSi has a calculated ionization potential of 8.07 eV in excellent agreement with the experimental value of 8.14 eV.