Benchmarking Cation−π Interactions: Assessment of Density Functional Theory and Möller–Plesset Second-Order Perturbation Theory Calculations with Optimized Basis Sets (mp2mod) for Complexes of Benzene, Phenol, and Catechol with Na+, K+, Rb+, and Cs+

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The reliability of several DFT functionals and of the Möller-Plesset Second Order Perturbation Theory Calculations with Modified Basis Sets (MP2mod) approach in describing cation-π interactions is systematically investigated by benchmarking their performances with respect to high quality reference CCSD(T) calculations of the binding energies between first group alkali ions (Na+, K+, Rb+ and Cs+ ) and three aromatic species (benzene, phenol and catechol). For this class of non-covalent interaction, MP2mod delivers, in average, results in very good agreement with the reference CCSD(T) data, yet at a very small computational cost, exploiting the reduced dimensions of the modified basis set. Conversely, the tested DFT functionals show a more erratic behaviour, with different performances depending on both the investigated system and the combination of the employed functional and basis set. The MP2mod computational convenience is further exploited to extensively sample two-dimensional interaction energy surfaces of all investigated cation-π systems, which allow for a deeper insight on the effect of the increasing number of hydroxyl substituents, revealing the insurgence, upon substitution, of alternative minima, evident in particular for the smaller cations. The present results are very encouraging for further applications of the MP2mod method to study a larger variety of aromatic/metal cation species, relevant both in biological processes and in technological applications.