10.26434/chemrxiv.7381943.v1
Adeayo Ajala
Vamsee K. Voora
Narbe Mardirossian
Filipp Furche
Francesco Paesani
Assessment of Density Functional Theory in Predicting Interaction Energies Between Water and Polycyclic Aromatic Hydrocarbons: From Water on Benzene to Water on Graphene
2018
ChemRxiv
polyaromatic hydrocarbons
graphene
water
molecular interactions
density functional theory
random phase approximation
coupled cluster theory
2018-11-27 15:12:20
article
https://chemrxiv.org/articles/Assessment_of_Density_Functional_Theory_in_Predicting_Interaction_Energies_Between_Water_and_Polycyclic_Aromatic_Hydrocarbons_From_Water_on_Benzene_to_Water_on_Graphene/7381943
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<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.
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