Using high-level ab initio calculations, the cooperativity effects between an aerogen-bonding
and a pnicogen- or chalcogen-bonding interactions are studied in ternary Y ··· PH2CN ··· ZO3 and
Y ··· SHCN ··· ZO3 complexes ( Y = NH3, N2 and Z = Ar, Kr, Xe). A detailed analysis of the structures,
interaction energies and bonding properties is performed on these systems. For each set of the
complexes, a favourable cooperativity is observed between Z ··· N and P/S ··· N interactions, especially
in complexes involving NH3 and XeO3 molecules. It is found that for a given Y or Z, the amount
of cooperativity effects in Y ··· PH2CN ··· ZO3 complexes are important than Y ··· SHCN ··· ZO3 ones. For
each ternary complex considered, the effect of a Z ··· N aerogen bond on a P/S ··· N bond is more pro-
nounced than that of a P/S ··· N bond on a Z ··· N bond. The mechanism of the cooperativity effects
in the ternary complexes is studied by electron density difference, quantum theory of atoms in
molecules and natural bond orbital analyses. The solvent effects are also studied on the interaction
energy and cooperativity of Z ··· N and P/S ··· N bonds in the ternary systems.