Benchmark calculations of water–acene interaction energies: Extrapolation to the water–graphene limit and assessment of dispersion–corrected DFT methods

Abstract

In a previous study (J. Phys. Chem. C, 2009, 113, 10242-10248) we used density functional theory based symmetry-adapted perturbation theory (DFT-SAPT) calculations of water interacting with benzene (C(6)H(6)), coronene (C(24)H(12)), and circumcoronene (C(54)H(18)) to estimate the interaction energy between a water molecule and a graphene sheet. The present study extends this earlier work by use of a more realistic geometry with the water molecule oriented perpendicular to the acene with both hydrogen atoms pointing down. We also include results for an intermediate C(48)H(18) acene. Extrapolation of the water-acene results gives a value of -3.0 +/- 0.15 kcal mol(-1) for the binding of a water molecule to graphene. Several popular dispersion-corrected DFT methods are applied to the water-acene systems and the resulting interacting energies are compared to results of the DFT-SAPT calculations in order to assess their performance.

Density Functional Theory (DFT) Study on the Ternary Interaction System of the Fluorinated Ethylene Carbonate, Li+ and Graphene Model

“…This is a small number of rings for modeling a finite graphene surface. However, recent theoretical calculations indicated that this size of graphene sheet can reasonably represent the electronic states of the graphene system [18][19][20][21]. Therefore, the present calculations would provide useful information on the ternary interaction system.…”

Perspective: Advances and challenges in treating van der Waals dispersion forces in density functional theory

“…It is also very encouraging that condensed phase reference systems are beginning to emerge, such as ice, LiH, water on LiH and water on graphene. 63,154,155,[157][158][159][160][161][162][163][164] By tackling these and other reference systems with the widest possible range of techniques we will better understand the limitations of existing dispersion-based DFT approaches, which will aid the development of more efficient and more accurate methods for the simulation of materials in general.…”

Water on BN doped benzene: A hard test for exchange-correlation functionals and the impact of exact exchange on weak binding

“…[17][18][19] Despite the growing number of studies for water on h-BN [20][21][22] and graphene 15,16,[23][24][25][26][27] there are no direct measurements of adsorption energies for the water monomer, and the theoretical adsorption energies for these systems vary significantly across different high accuracy methods. 25,[27][28][29] One can use smaller model systems for graphene 25,[29][30][31][32] and h-BN, such as benzene and the inorganic counterpart borazine (B 3 N 3 H 6 ), to help understand the interaction with water. With these small molecules, it is possible to use high accuracy methods to calculate benchmark interaction energies and binding conformations, [33][34][35][36][37] that would otherwise be infeasible for the extended surfaces.…”