Adsorption and decomposition of cyclohexanone (C6H10O) on Pt(111) and the (2 × 2) and (√3 × √3)r30°-Sn/Pt(111) surface alloys

Adsorption and decomposition of cyclohexanone (C(6)H(10)O) on Pt(111) and on two ordered Pt-Sn surface alloys, (2 × 2)-Sn/Pt(111) and (√3 × √3)R30°-Sn/Pt(111), formed by vapor deposition of Sn on the Pt(111) single crystal surface were studied with TPD, HREELS, AES, LEED, and DFT calculations with vibrational analyses. Saturation coverage of C(6)H(10)O was found to be 0.25 ML, independent of the Sn surface concentration. The Pt(111) surface was reactive toward cyclohexanone, with the adsorption in the monolayer being about 70% irreversible. C(6)H(10)O decomposed to yield CO, H(2)O, H(2), and CH(4). Some C-O bond breaking occurred, yielding H(2)O and leaving some carbon on the surface after TPD. HREELS data showed that cyclohexanone decomposition in the monolayer began by 200 K. Intermediates from cyclohexanone decomposition were also relatively unstable on Pt(111), since coadsorbed CO and H were formed below 250 K. Surface Sn allowed for some cyclohexanone to adsorb reversibly. C(6)H(10)O dissociated on the (2 × 2) surface to form CO and H(2)O at low coverages, and methane and H(2) in smaller amounts than on Pt(111). Adsorption of cyclohexanone on (√3 × √3)R30°-Sn/Pt(111) at 90 K was mostly reversible. DFT calculations suggest that C(6)H(10)O adsorbs on Pt(111) in two configurations: by bonding weakly through oxygen to an atop Pt site and more strongly through simultaneously oxygen and carbon of the carbonyl to a bridged Pt-Pt site. In contrast, on alloy surfaces, C(6)H(10)O bonds preferentially to Sn. The presence of Sn, furthermore, is predicted to make the formation of the strongly bound C(6)H(10)O species bonding through O and C, which is a likely decomposition precursor, thermodynamically unfavorable. Alloying with Sn, thus, is shown to moderate adsorptive and reactive activity of Pt(111).     

The three-body dissociation dynamics of Cl2O at 248 and 193 nm

The photodissociation of Cl₂O has been studied at 248 and 193 nm using photofragment translational spectroscopy (PTS) experiments with tunable VUV photoionization detection. The sole products observed were Cl, O and ClO fragments. Based on the derived translational energy distributions for the ClO and Cl photofragments we conclude that at 248 nm 15% of Cl₂O excitation results in three-body dissociation. At 193 nm no Cl₂ fragments are observed and we conclude that the oxygen atoms arise solely from three-body dissociation. Dissociation geometries derived from forward convolution fitting suggest two qualitatively distinct three-body dissociation pathways: asymmetric concerted dissociation and symmetric concerted dissociation in agreement with recent theoretical predictions.     

On the origin of the cation templated self-assembly of uranyl-peroxide nanoclusters

Uranyl-peroxide nanoclusters display different topologies based on square, pentagonal and hexagonal building blocks. Computed complexation energies of different cations (Li(+), Na(+), K(+), Rb(+), and Cs(+)) with [UO(2)(O(2))(H(2)O)](n) (n = 4, 5, and 6) macrocycles suggest a strong cation templating effect. The inherent bent structure of a U-O(2)-U model dimer is demonstrated and justified through the analysis of its electronic structure, as well as of the inherent curvature of the four-, five-, and six-uranyl macrocyles. The curvature is enhaced by cation coordination, which is suggested to be the driving force for the self-assembly of the nanocapsules.     

Noise control by sonic crystal barriers made of recycled materials

A systematic study of noise barriers based on sonic crystals made of cylinders that use recycled materials like absorbing component is reported here. The barriers consist of only three rows of perforated metal shells filled with rubber crumb. Measurements of reflectance and transmittance by these barriers are reported. Their attenuation properties result from a combination of sound absorption by the rubber crumb and reflection by the periodic distribution of scatterers. It is concluded that the porous cylinders can be used as building blocks whose physical parameters can be optimized in order to design efficient barriers adapted to different noisy environments.     

Majorana edge states in interacting one-dimensional systems

We show that one-dimensional electron systems in the proximity of a superconductor that support Majorana edge states are extremely susceptible to electron-electron interactions. Strong interactions generically destroy the induced superconducting gap that stabilizes the Majorana edge states. For weak interactions, the renormalization of the gap is nonuniversal and allows for a regime in which the Majorana edge states persist. We present strategies of how this regime can be reached.     

Photon-photon gates in Bose-Einstein condensates

It has recently been shown that light can be stored in Bose-Einstein condensates for over a second. Here we propose a method for realizing a controlled phase gate between two stored photons. The photons are both stored in the ground state of the effective trapping potential inside the condensate. The collision-induced interaction is enhanced by adiabatically increasing the trapping frequency and by using a Feshbach resonance. A controlled phase shift of π can be achieved in 1 s or less.     

Enhanced reactivity of nanoscale iron particles through a vacuum annealing process

A reactivity study was undertaken to compare and assess the rate of dechlorination of chlorinated aliphatic hydrocarbons (CAHs) by annealed and non-annealed nanoscale iron particles. The current study aims to resolve the uncertainties in recently published work studying the effect of the annealing process on the reduction capability of nanoscale Fe particles. Comparison of the normalized rate constants (m²/h/L) obtained for dechlorination reactions of trichloroethene (TCE) and cis-1,2-dichloroethene (cis-1,2-DCE) indicated that annealing nanoscale Fe particles increases their reactivity ~30-fold. An electron transfer reaction mechanism for both types of nanoscale particles was found to be responsible for CAH dechlorination, rather than a reduction reaction by activated H₂ on the particle surface (i.e., hydrogenation, hydrogenolysis). Surface analysis of the particulate material using X-ray diffraction (XRD) and transmission electron microscopy (TEM) together with surface area measurement by Brunauer, Emmett, Teller (BET) indicate that the vacuum annealing process decreases the surface area and increases crystallinity. BET surface area analysis recorded a decrease in nanoscale Fe particle surface area from 19.0 to 4.8 m²/g and crystallite dimensions inside the particle increased from 8.7 to 18.2 nm as a result of annealing.     

Optimum fiber tapers for increasing the power in the blue edge of a supercontinuum-group-acceleration matching

We demonstrate how the gradient of the tapering in a tapered fiber can significantly affect the trapping and blueshift of dispersive waves (DWs) by a soliton. By modeling the propagation of a fundamental 10?fs soliton through tapered fibers with varying gradients, it is shown that the soliton traps and blueshifts an increased fraction of the energy in its DW when the gradient is decreased. This is quantified by the group-acceleration mismatch between the soliton and DW at the entrance of the taper. These findings have direct implications for the achievable power in the blue edge of a supercontinuum generated in a tapered fiber and explain observations of a lack of power in the blue edge.     

Engineering the plasmon resonance of large area bimetallic nanoparticle films by laser nanostructuring for chemical sensors

Large area fabrication of metal alloy nanoparticles with tunable surface plasmon resonances on low-cost substrates is reported. A UV excimer laser was used to anneal 5 nm thick Ag Au bilayer films deposited with different composition ratios to create alloy nanoparticles. These engineered surfaces are used to investigate how the wavelength of the surface plasmon resonance affects the optical detection capability of chemical species by surface-enhanced Raman spectroscopy.     

XPS study of protein adsorption onto nanocrystalline aluminosilicate microparticles

X-ray photoelectron spectroscopy (XPS) was used to study the interaction of two different sized proteins, bovine serum albumin (BSA) and fibrinogen, with an aluminosilicate system containing yttrium and iron that is a potential biomaterial. Serum albumin and fibrinogen are two major plasma proteins and the most relevant proteins adsorbed on the surface of biomaterials in blood contact.The aluminosilicate samples were incubated for several exposure times, up to 24 h, in simulated body fluid enriched with BSA, and in buffered fibrinogen solution. Time dependence of proteins adsorption onto surface of the investigated samples is reflected by the evolution of the new N 1s photoelectron peak and by the modification of C 1s core-level spectra recorded from the samples immersed in protein solution.