A QM/MM approach for the study of monolayer-protected gold clusters

  title={A QM/MM approach for the study of monolayer-protected gold clusters},
  author={Sandipan Banerjee and John A Montgomery and Jos{\'e} A. Gasc{\'o}n},
  journal={Journal of Materials Science},
We report the development and implementation of hybrid methods that combine quantum mechanics (QM) with molecular mechanics (MM) to theoretically characterize thiolated gold clusters. We use, as training systems, structures such as Au25(SCH2–R)18 and Au38(SCH2–R)24, which can be readily compared with recent crystallographic data. We envision that such an approach will lead to an accurate description of key structural and electronic signatures at a fraction of the cost of a full quantum chemical… 
A Unified AMBER-Compatible Molecular Mechanics Force Field for Thiolate-Protected Gold Nanoclusters.
The presented parameter set contains the minimum number of cluster-specific parameters enabling the use of these parameters for several different gold nanoclusters, and the parameterization of ligands can also be extended to different types of ligand.
The Role of the Anchor Atom in the Ligand of the Monolayer-Protected Au25(XR)18– Nanocluster
We present a density functional theory (DFT) investigation on the role of the anchor atom and ligand on the structural, electronic, and optical properties of the anionic Au25(XR)18– nanocluster (X =
Thermal Conductivity of Gold–Phenylethanethiol (Au144PET60) Nanoarrays: A Molecular Dynamics Study
Solvated nanoarrays of Au144 nanoparticles capped with 60 phenylethanethiol (PET) moieties were studied using reverse nonequilibrium molecular dynamics (RNEMD) simulations. The thermal conductivities
Surface Dynamics and Ligand-Core Interactions of Quantum Sized Photoluminescent Gold Nanoclusters.
It is shown that the peptide sequence plays an important role in determining the surface peptide structuring, interfacial water dynamics and ligand-Au core interaction, which can be tailored by controlling peptide acetylation, constituent amino acid electron donating/withdrawing capacity, aromaticity/hydrophobicity and by adjusting environmental pH.
Connectivity-Based Biocompatible Force Field for Thiolated Gold Nanoclusters
Thiolated gold nanoclusters (AuNCs), sub-2 nm Au particles capped by Au(I) thiolate complexes, promise to have a myriad of applications in biomedical diagnosis and therapy as well as industrial
Ligand shell size effects on one- and two-photon excitation fluorescence of zwitterion functionalized gold nanoclusters.
Gold nanoclusters are an emerging class of luminescent nanomaterials but still suffer from moderate photoluminescence quantum yields, so introducing zwitterionic ligands to cap the metallic kernel is an efficient approach to enhance their one-photon excitation fluorescence intensity.
Understanding and Designing the Gold-Bio Interface: Insights from Simulations.
A perspective of the current successes and challenges associated with the multiscale computational treatment of Au-bio interfacial systems, from electronic structure calculations to force field methods, is provided to illustrate the links between different approaches and their relationship to experiment and applications.
Recent advances in first principles computations in materials research
The growing need to understand factors that govern the properties of materials, rapid strides in theory, and the wide availability of scientific software and computing resources has lead to an


Molecular Modeling Characterization of a Conformationally Constrained Monolayer-Protected Gold Cluster†
We present a multilevel molecular modeling study aimed at elucidating physical and chemical properties of gold clusters capped by a monolayer of thiolated oligopeptides. The protecting peptides are
Combining Quantum Mechanics Methods with Molecular Mechanics Methods in ONIOM.
The potential surface can be discontinuous when there is bond breaking and forming closer than three bonds from the MM region and the behavior of ONIOM with electronic embedding can be more stable than QM/MM with electronicembedding.
Structure of a Thiol Monolayer-Protected Gold Nanoparticle at 1.1 Å Resolution
The crystallization and x-ray structure determination of a p-mercaptobenzoic acid–protected gold nanoparticle, which comprises 102 gold atoms and 44 p-MBAs, is reported, which is chiral, with the two enantiomers alternating in the crystal lattice.
Structure and thermal stability of gold nanoclusters: The Au38 case
Abstract.Gold nanoclusters with disordered and ordered structures are obtained as the lowest-energy configurations of the cluster potential energy surface (PES) by unconstrained dynamical and
Effects of core distances, solvent, ligand, and level of theory on the TDDFT optical absorption spectrum of the thiolate-protected Au(25) nanoparticle.
  • C. Aikens
  • Chemistry
    The journal of physical chemistry. A
  • 2009
The size of the ligand plays a minor role on the optical absorption spectrum and solvent effects on geometries and excitation energies are negligible, which demonstrates that the core geometric and electronic structure is primarily responsible for the discrete optical absorption exhibited by this nanoparticle.
Experimental and Density Functional Theory Analysis of Serial Introductions of Electron-Withdrawing Ligands into the Ligand Shell of a Thiolate-Protected Au25 Nanoparticle
The progress of ligand exchange reactions between the ligands of Au25(SR)18− nanoparticles (SR = S(CH2)2Ph) and thiols with electron-withdrawing substituents (HSPh-p-X; X = Br, NO2) was monitored
Gold nanoclusters protected by conformationally constrained peptides.
The results showed that the chemical integrity of the peptide is maintained upon monolayer formation and that the average number of peptide ligands per gold cluster is typically 75-85% the value calculated for alkanethiolate MPCs of similar sizes.
On the structure of thiolate-protected Au25.
Density functional theory is used to explore the structure of Au25(RS)18 and the enhanced stability of the structure as an anion is found to originate from closure of an eight-electron shell for delocalized Au(6s) electrons.
Total structure determination of thiolate-protected Au38 nanoparticles.
The total structure of Au(38)(SC(2)H(4)Ph)(24) nanoparticles determined by single crystal X-ray crystallography is reported, which is based upon a face-fused Au(23) biicosahedral core and capped by three monomeric Au(SR)(2) staples at the waist of the Au( 23) rod.
Chirality and electronic structure of the thiolate-protected Au38 nanocluster.
The study demonstrates a new mechanism for the strong chiral response of thiolate-protected gold clusters with achiral metal cores and ligands with strong circular dichroism (CD) in the excitations below 2.2 eV.