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

Abstract

<div> <div> <div> <p>The interaction of water with polycyclic aromatic hydrocarbons, from benzene to graphene, is investigated using various exchange-correlation functionals selected across generalized gradient approximation (GGA), meta-GGA, and hybrid families within the density functional theory (DFT) hierarchy. The accuracy of the different functionals is assessed through comparisons with high-level electronic structure methods, including random phase approximation (RPA), diffusion Monte Carlo (DMC), and coupled-cluster with single, double, and perturbative triple excitations (CCSD(T)). Relatively large variations are found in the 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, and the meta-GGA B97M-rV and hybrid ωB97M-V functionals providing nearly quantitative agreement with CCSD(T) values available for the water-benzene, water-coronene, and water-circumcoronene dimers, which, in turn, are within ∼1 kcal/mol of the corresponding RPA and DMC results. Similar trends among GGA, meta-GGA, and hybrid functionals are observed for the larger polycyclic aromatic hydrocarbon molecules considered in this analysis (up to C216H36). By performing absolutely localized molecular orbital energy decomposition analyses (ALMO-EDA) of the DFT results, 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. Importantly, water-graphene interaction energies calculated with the B97M-rV functional appear to deviate by more than 1 kcal/mol from the available RPA and DMC values. </p> </div> </div> </div>

Divergence of Many-Body Perturbation Theory for Noncovalent Interactions of Large Molecules

“…The present results raise the question whether the perturbative triples correction of CCSD(T) inherits any of the limitations of MBPT, even though it includes some screening at the level of the amplitudes. Whereas CCSD(T) errors for interaction energies of small molecular complexes were determined to be on the order of 1%, 68 and typical deviations between RPA and CCSD(T) binding energies are on the order of 5-10% for the benchmarks studied here, the linear scaling domain-based pair natural orbital CCSD(T) binding energies for water on small graphene flakes are significantly larger than the corresponding RPA and diffusion Monte Carlo ones, 133 and the CCSD(T) perturbative triples correction diverges for the correlation energy of the uniform electron gas. 134 The AC-SAPT formalism developed here affords separate, non-perturbative definitions of dispersion and induction effects in NIs.…”