A theoretical screening of the O[sbnd]H⋅⋅⋅π interaction between water and benzene using density-functional approaches: Effects of nonlocal exchange and long-range dispersion corrections in the true minimum

Abstract

We employ different density-functional schemes to examine the specific OH⋅⋅⋅π interaction between benzene and water. We compare our results to second-order Møller-Plesset perturbation theory and quadratic configuration interaction, restricted to single and double substitutions. Using hybrid meta- and dispersion-corrected functionals, we explore the role of nonlocal exchange and dispersion interactions for the stabilization of the 1:1 complex. We also critically analyze the van der Waals fundamentals, and typical libration modes of bound water within these levels of calculations. Our results indicate that stringent criteria in the choice of the density-functional approach to describe this system are necessary, mainly if the interest goes beyond the small 1:1 complex.