A b i n i t i o correlated potential energy surfaces for monomeric sodium and potassium cyanides

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Abstract
Ab initio molecular orbital calculations using large Gaussian basis sets have been performed for NaCN and KCN with full geometry optimization. Potential energy surface obtained are sensitive to the quality of polarization functions used on C and N. A bent structure, as found experimentally for KCN, is the lowest energy geometry for both NaCN and KCN, with the isocyanide form only 5–6 kJ mol−1 higher at the SCF level. Inclusion of electron correlation using third‐order perturbation theory leads to a substantial relative destabilization of the isocyanide form for the both NaCN and KCN, and improves agreement between observed and theoretical geometries for KCN.