Logo image
Back
First-principles DFT modeling of nitrobenzene adsorption on the Ag(111) surface at varying monolayer coverages
Journal article   Peer reviewed

First-principles DFT modeling of nitrobenzene adsorption on the Ag(111) surface at varying monolayer coverages

Amelia K. Dodge and Sara E. Mason
Surface science, Vol.773, 123039
10/2026
DOI: 10.1016/j.susc.2026.123039

View Online

Abstract

•First-principles DFT modeling of nitrobenzene adsorption on the Ag(111) surface at varying monolayer coverages.•Nitrobenzene preferentially adsorbs to top sites on the Ag(111) surface via oxygen.•At higher coverages, adsorbate–adsorbate interactions can lead to cooperative or competing effects that significantly alter binding configurations and electronic properties.•Bidentate adsorption is favored at low and moderate coverages, and monodentate adsorption is favored at high coverage. The adsorption behavior of nitrobenzene on the Ag(111) surface as a function of coverage is investigated using density functional theory. Adsorption energies and optimized geometries are analyzed together with isolated intermolecular interaction calculations and electronic structure analysis, including Bader charge partitioning and projected density of states, to disentangle the roles of adsorbate–surface bonding and through-space adsorbate–adsorbate interactions. At low and intermediate coverages (θ = 1/9 and θ = 2/9), bidentate adsorption at top sites is favored due to strong adsorbate–surface interactions, with additional stabilization at θ = 2/9 arising from favorable intermolecular separations. At higher coverage (θ = 1/3), bidentate adsorption is destabilized by strong intermolecular repulsion, and monodentate adsorption becomes energetically preferred as rotational freedom allows more favorable intermolecular spacing. Charge density differences, Bader charge, and density of states analyses show that charge transfer from the Ag surface is localized primarily on the nitro group and increases with coverage and adsorption denticity, although this increase does not directly correlate with adsorption strength at high coverage due to competing intermolecular interactions. These results demonstrate that surface coverage can induce a transition in preferred adsorption denticity driven by intermolecular interactions, highlighting the importance of adsorbate packing in organic molecule adsorption at metal interfaces. [Display omitted]
 Adsorption Coverage Density functional theory Nitrobenzene

Details

Metrics

1 Record Views
Logo image