Effect of basis set superposition errors on complexation energies and molecular structures of various molecular complexes

초록

Polymer-based solid electrolytes have been the subject of intensive study because of their growing importance in solid-state electrochemistry. When two or more species form a complex, the interaction energy can be estimated from the energy difference between the whole system and its subunits within the supermolecular approach. In this case, the intermolecular descriptions between subunits can be improved by utilizing the basis functions of the partners, known as the basis set superposition error (BSSE).[1] We examined the effects of the BSSE corrections on the geometries and complexation energies for the organo-alkali metal cation complexes [2] and their iodide complexes. We found that the fCP correction was found to be inadequate and the incorporation of geometrical relation into the GCP method improved the results. When the structures were re-optimized on the CP-corrected potential energy surfaces, structural variations showed unusual trends. This phenomenon was examined in detail using various types of loose and tight binding complexes.