Intermolecular interactions between the heavy-atom analogues of acetylene T₂H₂ (T = Si, Ge, Sn, Pb) and HCN

The intermolecular interactions between the heavy-atom analogues of acetylene T₂H₂ (T = Si, Ge, Sn, Pb) and HCN have been investigated by theoretical calculations at the CCSD(T)/aug-cc-pVTZ//MP2/aug-cc-pVDZ level.

The global energy minimum of T₂H₂ is the butterfly structure A, and another energy minimum is the planar structure B. Both structures A and B exhibit the dual behavior when binding with HCN. The various hydrogen bond (HB), dihydrogen bond (DB) and tetrel bond (TB) complexes can be found according to the MEP maps of T₂H₂. One TB and three HB complexes formed between structure A and HCN can be located for Si₂H₂ and Ge₂H₂. One TB, two HB and one DB complexes formed between structure A and HCN can be located for Sn₂H₂ and Pb₂H₂. Four TB and one HB complexes formed between structure B and HCN can be located for all the T₂H₂. The geometries and binding strengths of the complexes are compared and analyzed.

The interactions in these complexes are generally weak, and the interaction energies of these complexes range from -0.53 to -8.23 kcal/mol. The interaction energies of the TB complexes are larger than those of the corresponding HB and DB complexes for structure A···HCN systems. The relative binding strength of the four TB complexes exhibits different order for different structure B···HCN systems, which is consistent with the MEP maps of the isolated monomers.