Uranium(III) coordination chemistry and oxidation in a flexible small-cavity macrocycle

U(III) complexes of the conformationally flexible, small-cavity macrocycle trans-calix[2]benzene[2]pyrrolide (L)2–, [U(L)X] (X = O-2,6-tBu2C6H3, N(SiMe3)2), have been synthesized from [U(L)BH4] and structurally characterized. These complexes show binding of the U(III) center in the bis(arene) pocket of the macrocycle, which flexes to accommodate the increase in the steric bulk of X, resulting in long U–X bonds to the ancillary ligands. Oxidation to the cationic U(IV) complex [U(L)X][B(C6F5)4] (X = BH4) results in ligand rearrangement to bind the smaller, harder cation in the bis(pyrrolide) pocket, in a conformation that has not been previously observed for (L)2–, with X located between the two ligand arene rings

Low-lying bifurcations in cavity quantum electrodynamics

The interplay of quantum fluctuations with nonlinear dynamics is a central topic in the study of open quantum systems, connected to fundamental issues (such as decoherence and the quantum-classical transition) and practical applications (such as coherent information processing and the development of mesoscopic sensors/amplifiers). With this context in mind, we here present a computational study of some elementary bifurcations that occur in a driven and damped cavity quantum electrodynamics (cavity QED) model at low intracavity photon number. In particular, we utilize the single-atom cavity QED Master Equation and associated Stochastic Schrodinger Equations to characterize the equilibrium distribution and dynamical behavior of the quantized intracavity optical field in parameter regimes near points in the semiclassical (mean-field, Maxwell-Bloch) bifurcation set. Our numerical results show that the semiclassical limit sets are qualitatively preserved in the quantum stationary states, although quantum fluctuations apparently induce phase diffusion within periodic orbits and stochastic transitions between attractors. We restrict our attention to an experimentally realistic parameter regime.Comment: 13 pages, 10 figures, submitted to PR

Infrared detection of concrete deterioration

Infrared detection of concrete deterioratio

Dynamical and quasistatic structural relaxation paths in Pd_(40)Ni_(40)P_(20) glass

By sequential heat treatment of a Pd_(40)Ni_(40)P_(20) metallic glass at temperatures and durations for which α-relaxation is not possible, dynamic, and quasistatic relaxation paths below the glass transition are identified via ex situ ultrasonic measurements following each heat treatment. The dynamic relaxation paths are associated with hopping between nonequilibrium potential energy states of the glass, while the quasistatic relaxation path is associated with reversible β-relaxation events toward quasiequilibrium states. These quasiequilibrium states are identified with secondary potential energy minima that exist within the inherent energy minimum of the glass, thereby supporting the concept of the sub-basin/metabasin organization of the potential-energy landscape

Photoemission electron microscopy of localized surface plasmons in silver nanostructures at telecommunication wavelengths

We image the field enhancement at Ag nanostructures using femtosecond laser pulses with a center wavelength of 1.55 micrometer. Imaging is based on non-linear photoemission observed in a photoemission electron microscope (PEEM). The images are directly compared to ultra violet PEEM and scanning electron microscopy (SEM) imaging of the same structures. Further, we have carried out atomic scale scanning tunneling microscopy (STM) on the same type of Ag nanostructures and on the Au substrate. Measuring the photoelectron spectrum from individual Ag particles shows a larger contribution from higher order photoemission process above the work function threshold than would be predicted by a fully perturbative model, consistent with recent results using shorter wavelengths. Investigating a wide selection of both Ag nanoparticles and nanowires, field enhancement is observed from 30% of the Ag nanoparticles and from none of the nanowires. No laser-induced damage is observed of the nanostructures neither during the PEEM experiments nor in subsequent SEM analysis. By direct comparison of SEM and PEEM images of the same nanostructures, we can conclude that the field enhancement is independent of the average nanostructure size and shape. Instead, we propose that the variations in observed field enhancement could originate from the wedge interface between the substrate and particles electrically connected to the substrate