Assessment of Density Functional Theory in Predicting Interaction Energies Between Water and Polycyclic Aromatic Hydrocarbons: From Water on Benzene to Water on Graphene

Abstract

The interactions of water with polycyclic aromatic hydrocarbons, from benzene to graphene, are investigated using various exchange-correlation functionals selected across the hierarchy of density functional theory (DFT) approximations. The accuracy of the different functionals is assessed through comparisons with random phase approximation (RPA) and coupled-cluster with single, double, and perturbative triple excitations [CCSD(T)] calculations. Diffusion Monte Carlo (DMC) data reported in the literature are also used for comparison. Relatively large variations are found in interaction energies predicted by different DFT models, with GGA functionals underestimating the interaction strength for configurations with the water oxygen pointing toward the aromatic molecules. The meta-GGA B97M-rV and range-separated hybrid, meta-GGA ωB97M-V functionals provide nearly quantitative agreement with CCSD(T) values for the water–benzene, water–coronene, and water–circumcoronene dimers, while RPA and DMC predict interaction energies that differ by up to ∼1 kcal/mol and ∼0.4 kcal/mol from the corresponding CCSD(T) values, respectively. Similar trends among GGA, meta-GGA, and hybrid functionals are observed for larger polycyclic aromatic hydrocarbons. By performing absolutely localized molecular orbital energy decomposition analyses (ALMO-EDA), it is found that, independently of the number of carbon atoms and exchange-correlation functional, the dominant contributions to the interaction energies between water and polycyclic aromatic hydrocarbon molecules are the electrostatic and dispersion terms while polarization and charge transfer effects are negligibly small. Calculations carried out with GGA and meta-GGA functionals indicate that, as the number of carbon atoms increases, the interaction energies slowly converge to the corresponding values obtained for an infinite graphene sheet.