Reliability of the density functional approximation to describe the charge transfer of electrostatic complexes involved in the modeling of organic conducting polymers

Abstract

Both the intermolecular interaction energies and the geometries for M ⋯ thiophene, M ⋯ pyrrole, M n + ⋯ thiophene, and M n + ⋯ pyrrole (with M = Li , Na, K, Ca, and Mg; and M n + = Li + , Na + , K + , Ca 2 + , and Mg 2 + ) have been estimated using four commonly used density functional theory (DFT) methods: B3LYP, B3PW91, PBE, and MPW1PW91. Results have been compared to those provided by HF, MP2, and MP4 conventional ab initio methods. The PBE and MPW1PW91 are the only DFT methods able to provide a reasonable description of the M ⋯ π complexes. Regarding M n + ⋯ π complexes, the four DFT methods have been proven to be adequate in the prediction of these electrostatically stabilized systems, even though they tend to overestimate the interaction energies.