Adsorption of atomic and molecular monolayers on Pt-supported graphene

CO2 on Graphene: Benchmarking Computational Approaches to Noncovalent Interactions

“…In fact, while other methods, such as nonlocal van der Waals periodic computations (−25.1 kJ mol –1 on Pt(111) and −23.3 kJ mol –1 on SiC(0001) for bridge parallel orientation at the optB86b-vdW level) or extrapolated SAPT0 values corrected for the support effects (e.g., −23.6 kJ mol –1 on Pt(111) and −21.6 kJ mol –1 on SiC(0001) for bridge parallel orientation using the optB88-vdW corrections), predict more stable adsorptions, i.e., are closer to the experimental values, none of the methods reproduces the key experimental observationsthat CO 2 adsorbs on Pt-supported graphene in a tilted manner (corresponding to the orthogonal orientation in our models) and that adsorption on graphene on silica carbide in low-coverage regime is more exothermal than on a platinum support. Overall, these findings are in a stark contrast to the results obtained by Stachová et al, whose DFT results are within only 1.9 kJ mol –1 in terms of mean absolute errors from experiment.…”

“…Interaction Energies (in kJ mol −1 ) of CO 2 Adsorbed on Periodic Bare Graphene and on Periodic Single-Layer Graphene Deposited on Silica Carbide and Platinum Supports a stabilization of CO 2 adsorbate with GGA functionals and between 0.5 and 3.3 kJ mol −1 with nonlocal vdW functionals. These results are in a very good agreement with a recent study investigating adsorption of small molecules other than CO 2 on free-standing Pt(111)-supported graphene 18. Stabilization on silica carbide is mostly smaller, e.g., 0.3−2.1 kJ mol −1 at the GGA level and 0.5−1.8 kJ mol −1 at the nonlocal vdW level.…”

Toward accurate modeling of structure and energetics of bulk hexagonal boron nitride

“…37 Some studies have addressed the accuracy of different van der Waals (vdW) correction schemes, 37,38 while others have attempted to use more accurate methods for describing the interlayer interactions, 34 but to establish a good and general functional is a hard task, especially when small contributions coming from the dispersive components are the key ingredient to determine the exfoliation energy. 39 For a long time, vdW-corrected DFT remained the most accurate and reliable method for the calculation of weak interactions in periodic systems 37,40,41 with the typical high accuracy methods such as Møller-Plesset perturbation theory (MP2), 42,43 the random phase approximation (RPA), [44][45][46][47] or coupled cluster methods [48][49][50][51] being implemented only relatively recently and have seen little use due to their high computational demands.…”

“…In this respect, a promising ab initio approach that can readily treat periodic systems without the need to resort to many-body expansion techniques is the fixed-node diffusion Monte Carlo (FNDMC), a quantum Monte Carlo (QMC) method. 41,[52][53][54][55] An additional benefit of this method for (here essential) noncovalent systems is its accuracy, often comparable to that of the coupled cluster singles, doubles, and perturbative triples CCSD(T) method. 54,56,57 Although h-BN has been thoroughly studied computationally as well as experimentally, for some of its basic characteristics such as the exfoliation energy, no experimental estimates are currently available and theoretical models provide inconsistent results (21-39 meV/ atom).…”

“…For a long time, vdW‐corrected DFT remained the most accurate and reliable method for the calculation of weak interactions in periodic systems 37,40,41 with the typical high accuracy methods such as Møller‐Plesset perturbation theory (MP2), 42,43 the random phase approximation (RPA), 44‐47 or coupled cluster methods 48‐51 being implemented only relatively recently and have seen little use due to their high computational demands.…”