First-principles molecular dynamics simulations of the H2O / Cu(111) interface

Abstract

A first-principles theoretical study of the water-Cu(111) interface based on density functional calculations is reported. Using differently sized surface models: p(2 × 2), p(4 × 4) and p(4 × 5), we found out that the adsorption energy of a H(2)O monomer does not significantly change with the surface model though the adsorption geometry is sensitive to the choice of the super-cell surface and, also, to the coverage. Molecular dynamics simulations on the Born-Oppenheimer surface of liquid water on a Cu(111) surface reveal that H(2)O in the first solvent layer adsorbs O-down and that the H-bond network is weaker upon adsorption on the Cu. Furthermore, absolute electrochemical potentials are presented and compared to the potential of zero charge obtained experimentally and theoretically.

Interaction of H2O and H2S with Cu(111) and the impact of the electric field: the rotating & translating adsorbate, and the rippled surface

“…It was previously mentioned that the lateral size of the cell in this work is larger than any of the reported results. The results are in much better agreement if we compare our results with that of the work employing the next largest lateral size 11,17,31 . In particular, the adsorption energy and geometry of water found in this work and by Nadler and Sanz 31 are almost the same.…”

“…The most stable adsorbed structures of the monomers are determined through structural optimization computations using various initial orientations of the monomers on the atop site. A comparison between the adsorbed structures and adsorption energies of H 2 O and H 2 S at the atop site determined in the present work and previous work by others 4,10,11,17,[31][32][33] is shown in Table 3. E ads is the adsorption energy in eV.…”

Capturing Solvation Effects at a Liquid/Nanoparticle Interface by Ab Initio Molecular Dynamics: Pt201 Immersed in Water

“…The interaction of multilayers of water in contact with a metallic surface (from single molecule adsorption to ice‐monolayers, bilayers, etc.) has been studied several times during the last decades . Multiple forms of adsorption have been examined (from monomers to heptamers and multiple bilayers) with density functional theory (DFT) calculations .…”

“…On Pt(111), the variation of the adsorption energy from monomer (flat chemisorption through the oxygen atom on top sites) to multiple bilayers (including H‐up and H‐down adsorption configurations) is in the range 0.3–0.6 eV . Crossing over different metallic surfaces, the adsorption strength of the monomer changes from 0.1 to 0.4 eV . The adsorption strength of the monomer is also significantly modified when different exchange–correlation functionals are considered (from 0.01 to 0.47 eV) .…”

“…[ 15,17,[22][23][24][25][26][27] Multiple forms of adsorption have been examined (from monomers to heptamers and multiple bilayers) with density functional theory (DFT) calculations. [ 23 ] The infl uence of the metal [23][24][25]27 ] and the choice of the methodology [ 2,26,27 ] have also been investigated. On Pt(111), the variation of the adsorption energy from monomer (fl at chemisorption through the oxygen atom on top sites) to multiple bilayers (including H-up and H-down adsorption confi gurations) is in the range 0.3-0.6 eV.…”