Theoretical insight into cooperativity in lithium-bonded complexes: Linear clusters of LiCN and LiNC

Abstract

Ab initio calculations were used to analyze intermolecular interactions in linear clusters of (LiCN)n and (LiNC)n (n=2–7) which are connected via lithium bonds. Molecular geometries, binding energies, and cooperativity of title clusters are investigated at the MP2/6-311++G** and M06-2X/6-311++G** levels. Based on the energy decomposition analysis (EDA), it can be seen that the stabilities of the LiCN and LiNC clusters are predicted to be attributable mainly to electrostatic and polarization effects, while dispersion forces play a smaller role in stabilizing these clusters. Size dependent variation in atomic multipole moments should serve as a useful signature of lithium-bonding cooperativity of the title clusters.