Theoretical study of alkali cation-benzene complexes: Potential energy surfaces and binding energies with improved results for rubidium and cesium

High level ab initio quantum chemical calculations have been carried out on the binding of alkali metal to benzene with special attention to heavier metals for which the agreement between the most recent theoretical investigations and the experimental bond dissociation energies (BDEs) is not very good. We performed BSSE-corrected geometry optimizations employing the MP2 level of theory with large basis sets and a modified Stuttgart RSC 1997 basis set for rubidium and cesium and carried out single point energy calculations at the MP4 level, obtaining, also for the latter metals, BDE values in good agreement with the experimental results. Furthermore, in view of the development of empirical correction terms to force fields to describe cation-pi interactions, we evaluated the potential energy surface along the benzene symmetry axis and discussed the role of the BSSE correction on the accuracy of our results.