0000000000448571
AUTHOR
Michael J. Hartmann
Copper Induces a Core Plasmon in Intermetallic Au(144,145)–xCux(SR)60 Nanoclusters
The electronic structure and optical absorption spectra of intermetallic thiol-stabilized gold-copper clusters, having 144-145 metal atoms and 60 thiols, were studied by ab initio computations. The widely known icosahedral-based cluster model from the work of Lopez-Acevedo et al. (2009) was used, and clusters doped with one to 30 copper atoms were considered. When doped inside the metal core, copper induces dramatic changes in the optical spectrum as compared to the previously studied all-gold Au144(SR)60. An intense broad absorption peak develops in the range 535-587 nm depending on the amount of doping and doping sites. This result agrees very well with recent experiments by the Dass grou…
Spontaneous, collective coherence in driven, dissipative cavity arrays
We study an array of dissipative tunnel-coupled cavities, each interacting with an incoherently pumped two-level emitter. For cavities in the lasing regime, we find correlations between the light fields of distant cavities, despite the dissipation and the incoherent nature of the pumping mechanism. These correlations decay exponentially with distance for arrays in any dimension but become increasingly long ranged with increasing photon tunneling between adjacent cavities. The interaction-dominated and the tunneling-dominated regimes show markedly different scaling of the correlation length which always remains finite due to the finite photon trapping time. We propose a series of observables…
Impacts of Copper Position on the Electronic Structure of [Au25-xCux(SH)18]− Nanoclusters
Here, we use density functional theory to model the impact of heteroatom position on the optoelectronic properties of mixed metal nanoclusters. First, we consider the well-described [Au25(SH)18]− motif, and substitute Cu atoms at the three geometrically unique positions within the cluster. These clusters are atomically precise and show an electronic structure that is a function of both composition and heteroatom position. We then model clusters containing Cu substitutions at two positions, and demonstrate an additional and significant impact from heteroatom proximity with respect to one another. For each system, we report the formation energy, HOMO–LUMO gap, and energy level structure, and …
Surface Chemistry Controls Magnetism in Cobalt Nanoclusters
Magnetic properties of Co13 and Co55 nanoclusters, passivated by surface ligand shells that exhibit varying electronic interactions with the metal, are studied using density functional theory. The calculations show that the chemical nature of the bond between the ligand and the metal core (X-type or L-type) impacts the total magnetic moment of Co nanoclusters dramatically. Furthermore, the chemical identity of the ligand within each binding motif then provides a fine handle on the exhibited magnetic moment of the cluster. Thus, ligand shell chemistry is predicted to not only stabilize Co nanoclusters, but provide a powerful approach to control their magnetic properties, which combined enabl…
Ligand mediated evolution of size dependent magnetism in cobalt nanoclusters.
We use density functional theory to model the impact of a ligand shell on the magnetic properties of CoN (15 ≤ N ≤ 55) nanoclusters. We study three different ligand shells on each nanocluster core size, each known to have different electronic interactions with the surface: pure Cl ligand shells (X-type), pure PH3 ligand shells (L-type), and two component ligand shells with mixtures of Cl and PH3 ligands. The simulations show that the identity, arrangement, and total coverage of the ligand shell controls the distribution of local magnetic moments across the CoN core. On the surface of an unpassivated CoN nanocluster, the Co-Co coordination number (CN) is known to determine the local magnetic…