Systematic study of the adsorption of thiol molecules on a Au₅₅ nanoparticle

Abstract

In this work, we studied computationally the adsorption of methyl‐thiol molecules (SCH3) on a Au55 nanoparticle (NP) using spin‐polarized density functional theory (DFT) calculations within the generalized gradient approximation (GGA) as implemented in the SIESTA code (). Different conformations of SCH3 –Au55 system and SCH3 rotations were considered for the adsorption sites. We examined which adsorption sites of these clusters are preferentially occupied by the SCH3 molecule. According to our calculations, the bridge site is the overall favoured site for the molecule to be adsorbed independently of their initial configuration. The analysis of the structural properties of both NPs and molecules upon the adsorption process shows that NPs experience only a subtle atomic rearrangement due to the strong binding affinity between the sulphur terminal in the SCH3 and Au surface. The initial orientation of the SCH3 after the adsorption significantly changes affecting the adsorption energy.

Non-covalent adsorption of amino acid analogues on noble-metal nanoparticles: influence of edges and vertices

“…Our calculations differ from many previously reported FP studies of both covalent and non-covalent adsorption on NMNPs 20,[46][47][48][49][50][51][53][54][55][56][57][61][62][63] in two key aspects. First, we considered nanometer-sized Au 147 and Pt 147 cuboctahedral nanoparticles in our FP calculations, with vertex-to-vertex dimensions of 1.72 nm and 1.66 nm, respectively, where most previous studies considered much smaller nanoclusters.…”

“…Previously, FP calculations have been used to study the shape and the structure of NMNPs [39][40][41][42][43][44][45] as well as the covalent attachment of ligands to NMNP surfaces. 19,20,[46][47][48][49][50][51][52][53][54][55] The use of FP calculations to investigate the non-covalent adsorption of molecules to NMNPs has not been extensively reported. 51,[56][57][58] Of these few earlier studies, all used standard generalised-gradient approximation (GGA) density functionals, which are known to perform poorly in such weakly bound cases, 59,60 and/or were based on much smaller (sub-nanometer) NP sizes.…”

Improving Polymer/Nanocrystal Hybrid Solar Cell Performance via Tuning Ligand Orientation at CdSe Quantum Dot Surface

“…43 Hence, a comprehensive modeling, taking into account the curvature effect, the presence of nearby particles and intercrystal binding will provide more accurate information about the BDT binding modes. 5,45 However, it is beyond the scope of this manuscript. For the effect of internanocrystals connection, Sargent et al employed grazing-incidence smallangle X-ray scattering (GISAXS) to measure the interparticle distance of PbS nanocrystal films and found that mercaptopropionic acid, a bidentate organic cross-linker, can reduce the average center-to-center nanocrystal distance by cross-linking in the pure PbS films.…”

Understanding and Designing the Gold–Bio Interface: Insights from Simulations

“…In addition to static structure determination, QM methods may also be used to investigate the dynamics of AuNP formation, including aspects such as self‐assembly/aggregation, doping, metal oxidation, ligand exchange,[16a,39,51] and the binding of small molecules to gold surfaces and nanoclusters …”