A General Method for Structure Prediction of Metal-Ligand Interfaces of Hybrid Nanoparticles

<p>Here, we devise and validate a general method to predict the atomistic structure of the metal-ligand interface of thiol-stabilized gold nanoparticles Au<sub>x</sub>(SR)<sub>y</sub> by using information about gold-thiol chemical bonding in a set of reference structures documented from experiments. Our method is successful in predicting the observed Au-S interfacial structure for a range of different Au<sub>x</sub>(SR)<sub>y</sub> particles with (x,y) = (36,24), (38,24), (102,44), (146,57), and (279,84), starting from the known structure of the gold core. In addition to predicting realistic interface structures, our method may prove to be useful for investigations on how the steric effects in the ligand layer affect the metal-ligand interface, as well as for predicting isomers and intermediate structures during cluster transformations induced by thermal dynamics or interactions with the environment. Our method is, in principle, easily modifiable for structural predictions of a large variety of hybrid nanomaterial systems once a suitable set of reference structures is available. </p>