Benchmark calculations of the adsorption of aromatic molecules on graphene

Abstract

Selecting the saturated graphene fragment as a model of graphene, we have investigated seven popular density functionals, including ωB97X-D, B97-D, B-LYP-D3, M05-2X, M06-2X, M11-L, and N12, for their performance in describing the adsorption of aromatic molecules on graphene. The best performing functionals are B97-D, B-LYP-D3, and ωB97X-D. M05-2X, M06-2X, and M11-L significantly underestimate the adsorption strengths, while N12 fails completely in this respect. The effects of the basis sets and size of the saturated graphene fragments on the geometries, energies, and properties for the adsorption of aromatic molecules on graphene have also been studied. It was found that the small basis sets such as 6-31G(d) and jun-cc-pVDZ are not suitable for the accurate description of the adsorption of aromatic molecules on graphene. The size of selected graphene fragments has a little effect on both the ωB97X-D and SCS-SAPT0 interaction energies, but the effects of the size of selected graphene fragments on the energy components are significant in some cases of the adsorption of aromatic molecules on graphene. The surprising weakness of electrostatic interactions by F substitution for the adsorption of F-substituted benzenes on graphene was explained using the energy component analysis.

Ab Initio and DFT Studies on CO2 Interacting with Znq+–Imidazole (q=0, 1, 2) Complexes: Prediction of Charge Transfer through σ‐ or π‐Type Models

“…For instance, M11 predicts distinctly shorter Zn–N distances (by ≈0.4–0.5 Å). This might be related to its limited capability to describe accurately London‐dispersion interactions, as pointed out recently by Mardirossian and Head‐Gordon, DiLabio and Otero‐de‐la‐Roza and Wang et al . and established by Goerigk .…”

Calculations of adsorption energies, coadsorptions, and diffusion barriers of H atoms, and the H2 formation on a nanographene surface (coronene)

“…Details of the DFT calculations for diffusion barriers of H atoms on Cor is presented elsewhere . The use of dispersion corrections and the TZVP basis is well justified for the modeling of interactions on graphene surfaces …”

“…[61] The use of dispersion corrections and the TZVP basis is well justified for the modeling of interactions on graphene surfaces. [68][69][70] Because the carbonaceous material is one of the main constituents of interstellar grains, a surface model, such as Cor (C 24 H 12 ), [3,4] which has been used to simulate graphite, graphene, and PAH interstellar grains, was used as a model. This molecule, shown in Figure 1A, has been widely used for several authors [23][24][25]27,29,30,32,36,50,[71][72][73][74][75][76][77][78] and for our group [21,41,42,61] as a PAH model of ISM.…”

Combined molecular and periodic DFT analysis of the adsorption of co macrocycles on graphene

“…We, thus, describe here a theoretical DFT investigation of electronic properties of Co(II) porphyrin (CoP) or phthalocyanine (CoPc) adsorbed on monolayer and bilayer graphene substrates, based on either periodical or “molecular” quantum theoretical approaches. The purpose is not to propose a benchmark of the best methods to describe the adsorption of an aromatic molecule on a graphene sheet, as recent studies already exist in the literature . The aim is twofold, one being to decipher how the choice of calculation parameters influences the final values of interaction energy or geometry.…”

“…The purpose is not to propose a benchmark of the best methods to describe the adsorption of an aromatic molecule on a graphene sheet, as recent studies already exist in the literature. [49,50,[61][62][63][64][65] The aim is twofold, one being to decipher how the choice of calculation parameters influences the final values of interaction energy or geometry. The second objective is to describe the electronic properties of CoP or CoPc on a monolayer or bilayer of graphene, thanks to periodical (given by projected DOS) or "molecular" approaches (given by Kohn-Sham orbital diagrams).…”