Argon Interaction with Gold Surfaces: Ab Initio-Assisted Determination of Pair Ar–Au Potentials for Molecular Dynamics Simulations

Abstract

Global potentials for the interaction between the Ar atom and gold surfaces are investigated and Ar-Au pair potentials suitable for molecular dynamics simulations are derived. Using a periodic plane-wave representation of the electronic wave function, the nonlocal van-der-Waals vdW-DF2 and vdW-OptB86 approaches have been proved to describe better the interaction. These global interaction potentials have been decomposed to produce pair potentials. Then, the pair potentials have been compared with those derived by combining the dispersionless density functional dlDF for the repulsive part with an effective pairwise dispersion interaction. These repulsive potentials have been obtained from the decomposition of the repulsive interaction between the Ar atom and the Au2 and Au4 clusters and the dispersion coefficients have been evaluated by means of ab initio calculations on the Ar+Au2 complex using symmetry adapted perturbation theory. The pair potentials agree very well with those evaluated through periodic vdW-DF2 calculations. For benchmarking purposes, CCSD(T) calculations have also been performed for the ArAu and Ar+Au2 systems using large basis sets and extrapolations to the complete basis set limit. This work highlights that ab initio calculations using very small surface clusters can be used either as an independent cross-check to compare the performance of state-of-the-art vdW-corrected periodic DFT approaches or, directly, to calculate the pair potentials necessary in further molecular dynamics calculations.

Transferability and accuracy by combining dispersionless density functional and incremental post-Hartree-Fock theories: Noble gases adsorption on coronene/graphene/graphite surfaces

“…13 Very recently, this dlDF +D as scheme has been applied to get the pair interaction potentials which are necessary to simulate the flow of rare gases on gold surfaces. 23 This work is mainly aimed to analyze if the good performance of the periodic dlDF + incremental D * as /D as approaches for helium can be generalized to the rest of the noble-gas atoms. For this purpose, we have considered the Ne, Ar, Kr, and Xe atoms (collectively denoted as X atoms), and the graphene and graphite surfaces.…”

Nonclassical trajectories in head-on collisions

“…These effects will be more prominent at higher energies and must be accounted for by an inclusion of exchange terms in the Hamiltonian [35,36,37]. An even fuller approach would be to replace the Coulomb potential with more realistic interactions [38,39,40].…”

The Influence of Gas–Wall and Gas–Gas Interactions on the Accommodation Coefficients for Rarefied Gases: A Molecular Dynamics Study

“…as well as existing ab-initio pair potentials [22,28], derived from computational quantum mechanics. The detailed gas-gas and gases-Au interatomic potential parameters used for mixing rules are presented in Table 1.…”