摘要： We simulate the packing of citrate3– and H2citrate– onto gold nanoparticles (AuNPs) to understand how citrate anions cap and stabilize AuNPs. We determine the molecular configurations of citrate on 4, 6, and 8 nm AuNP surfaces as a function of charge state and packing density and find that both the distribution of configurations and maximum packing density are independent of AuNP size. A combination of molecular dynamics simulations and in situ Fourier transform infrared spectroscopy (FTIR) is employed to compare the molecular configurations, stability, and density of citrate on 4 nm citrate-coated (cit-AuNPs) and within polycation-wrapped 4 nm cit-AuNPs. FTIR experiments indicate the presence of H2citrate– within polycation-wrapped cit-AuNPs with coordination between the H2citrate– layer and polycation layer in agreement with simulations. Intermolecular hydrogen bonding between terminal carboxylic-acid groups of H2citrate– stabilizes the anionic layer at the interface between cit-AuNPs and adsorbing charged molecules. The calculated total density of H2citrate– on AuNPs decreases from 3.3 × 10-10 mol/cm2 to 3.0 × 10-10 mol/cm2 upon adsorption of a polycation due to some displacement of dangling H2citrate– hydrogen bonded to the surface-bound layer. The density of the surface-bound layer is consistently 2.8 × 10-10 mol/cm2 with and without polycation adsorption. We provide all-atom level insight into the distribution and organization of experimentally derived binding modes of citrate on bare and coated cit-AuNPs. The citrate density and surface charge density are determined for all-atom and coarse-grained modeling of cit-AuNPs, their functionalization, and transformations in complex environments.