Quantitative analysis of charge transfer plasmons in silver nanocluster dimers using semiempirical methods.

Plasmonic metal nanoclusters are widely used in chemistry, nanotechnology, and biomedicine. In metal nanocluster dimers, coupling of the plasmons leads to the emergence of two distinct types of modes: (1) bonding dipole plasmons (BDP), which occurs when charge oscillates synchronously within each nanocluster, and (2) charge transfer plasmons (CTP), which occurs when charge oscillates between two conductively linked nanoclusters. Although TDDFT-based modeling has uncovered some trends in these modes, it is computationally expensive for large dimers, and quantitative analysis is challenging.

Hydride- and halide-substituted Au(PH) nanoclusters: similar absorption spectra disguise distinct geometries and electronic structures.

Ligands dramatically affect the electronic structure of gold nanoclusters (NCs) and provide a useful handle to tune the properties required for nanomaterials that have high performance for important functions like catalysis. Recently, questions have arisen about the nature of the interactions of hydride and halide ligands with Au NCs: hydride and halide ligands have similar effects on the absorption spectra of Au NCs, which suggested that the interactions of the two classes of ligands with the Au core may be similar. Here, we elucidate the interactions of halide and hydride ligands with phosphine-protected gold clusters via theoretical investigations.

Direct Anti-Markovnikov Addition of Water to Olefin To Synthesize Primary Alcohols: A Theoretical Study.

Anti-Markovnikov addition of water to olefins has been a long-standing goal in catalysis. The [Rh(COD)(DPEphos)] complex was found as a general and regioselective group 9 catalyst for intermolecular hydroamination of alkenes. The reaction mechanism was adapted for intermolecular hydration of alkenes catalyzed by a [Rh(DPEphos)] catalyst and studied by DFT calculations.

Computational Analysis of Transition Metal-Terminal Boride Complexes.

A computational analysis of model transition-metal terminal boride [MB(PNP)] complexes is reported. A combination of density functional theory methods, natural bond orbital analysis, and multiconfiguration self-consistent field calculations were employed to investigate the structure and bonding of terminal boride complexes, in particular, the extent of metal dπ-boron pπ bonding. Comparison of metal-boride, -borylene, and-boryl bond lengths confirms the presence of metal-boron π bonds, albeit the modest shortening (∼3%) of the metal-boron bond suggests that the π-bonding is very weak in terminal borides.

Heterobimetallic Silver-Iron Complexes Involving Fe(CO) Ligands.

Iron(0) pentacarbonyl is an organometallic compound with a long history. It undergoes carbonyl displacement chemistry with various donors (L), leading to molecules of the type Fe(CO)(L). The work reported here illustrates that Fe(CO) can also act as a ligand.