Energy distribution analysis of the wavepacket simulations of CH4 and CD4 scattering

The isotope effect in the scattering of methane is studied by wavepacket simulations of oriented CH4 and CD4 molecules from a flat surface including all nine internal vibrations. At a translational energy up to 96 kJ/mol we find that the scattering is still predominantly elastic, but less so for CD4. Energy distribution analysis of the kinetic energy per mode and the potential energy surface terms, when the molecule hits the surface, are used in combination with vibrational excitations and the corresponding deformation. They indicate that the orientation with three bonds pointing towards the surface is mostly responsible for the isotope effect in the methane dissociation.Comment: 20 pages LaTeX, 1 figure (eps), to be published in Surf. Sc

High-Power 1180-nm GaInNAs DBR Laser Diodes

We report high-power 1180-nm GaInNAs distributed Bragg reflector laser diodes with and without a tapered amplifying section. The untapered and tapered components reached room temperature output powers of 655 mW and 4.04 W, respectively. The diodes exhibited narrow linewidth emission with side-mode suppression ratios in the range of 50 dB for a broad range of operating current, extending up to 2 A for the untapered component and 10 A for the tapered component. The high output power is rendered possible by the use of a high quality GaInNAs-based quantum well gain region, which allows for lower strain and better carrier confinement compared with traditional GaInAs quantum wells. The development opens new opportunities for the power scaling of frequency-doubled lasers with emission at yellow–orange wavelengths.publishedVersionPeer reviewe

Direct Evidence for the Participation of Oxygen Vacancies in the Oxidation of Carbon Monoxide over Ceria‐Supported Gold Catalysts by using Operando Raman Spectroscopy

Supported gold catalysts are highly active for a variety of reactions, including low‐temperature CO oxidation. It has been shown that reducible support materials, for example, ceria and titania, may significantly alter catalytic performance. However, the current understanding of the CO oxidation mechanism of such gold catalysts is still incomplete, as important details such as the activation of oxygen and the role of oxygen vacancies are unknown. To elucidate the role of the ceria support during room‐temperature CO oxidation, we employed operando Raman spectroscopy by simultaneously recording the Raman spectra of the catalyst and the gas‐phase FTIR spectra. Our results give first direct spectroscopic evidence for the participation of oxygen vacancies in the oxidation of CO over ceria‐supported gold, which thus underlines the crucial role of the support material for detailed understanding of the mode of operation of supported gold catalysts.Phantom of the opera‐ndo: By using operando Raman spectroscopy, direct spectroscopic evidence for the participation of oxygen vacancies in the oxidation of CO over ceria‐supported gold catalysts at room temperature is provided. The results underline the crucial role of the support material for detailed understanding of the mode of operation of supported gold catalysts.Peer Reviewedhttps://deepblue.lib.umich.edu/bitstream/2027.42/137587/1/cctc201501129-sup-0001-misc_information.pdfhttps://deepblue.lib.umich.edu/bitstream/2027.42/137587/2/cctc201501129.pd

Aromaticity in a Surface Deposited Cluster: Pd4_4 on TiO2_2 (110)

We report the presence of \sigma-aromaticity in a surface deposited cluster, Pd$_4$ on TiO$_2$ (110). In the gas phase, Pd$_4$ adopts a tetrahedral structure. However, surface binding promotes a flat, \sigma-aromatic cluster. This is the first time aromaticity is found in surface deposited clusters. Systems of this type emerge as a promising class of catalyst, and so realization of aromaticity in them may help to rationalize their reactivity and catalytic properties, as a function of cluster size and composition.Comment: 4 pages, 3 figure

Charge carrier dynamics in tantalum oxide overlayered and tantalum doped hematite photoanodes

We employ atomic layer deposition to prepare 50 nm thick hematite photoanodes followed by passivating them with a 0.5 nm thick Ta2O5-overlayer and compare them with samples uniformly doped with the same amount of tantalum. We observe a three-fold improvement in photocurrent with the same onset voltage using Ta-overlayer hematite photoanodes, while electrochemical impedance spectroscopy under visible light irradiation shows a decreased amount of surface states under water splitting conditions. The Tadoped samples have an even higher increase in photocurrent along with a 0.15 V cathodic shift in the onset voltage and decreased resistivity. However, the surface state capacitance for the Ta-doped sample is twice that of the reference photoanode, which implies a larger amount of surface hole accumulation. We further utilize transient absorption spectroscopy in the sub-millisecond to second timescale under operating conditions to show that electron trapping in both Ta2O5-passivated and Ta-doped samples is markedly reduced. Ultrafast transient absorption spectroscopy in the sub-picosecond to nanosecond timescale shows faster charge carrier dynamics and reduced recombination in the Ta-doped hematite photoanode resulting in the increased photoelectrochemical performance when compared with the Ta2O5-overlayer sample. Our results show that passivation does not affect the poor charge carrier dynamics intrinsic to hematite based photoanodes. The Ta-doping strategy results in more efficient electron extraction, solving the electron trapping issue and leading to increased performance over the surface passivation strategy.Peer reviewe

Stability of gold nanowires at large Au-Au separations

The unusual structural stability of gold nanowires at large separations of gold atoms is explained from first-principles quantum mechanical calculations. We show that undetected light atoms, in particular hydrogen, stabilize the experimentally observed structures, which would be unstable in pure gold wires. The enhanced cohesion is due to the partial charge transfer from gold to the light atoms. This finding should resolve a long-standing controversy between theoretical predictions and experimental observations.Comment: 7 pages, 3 figure

Au/TiO2(110) interfacial reconstruction stability from ab initio

We determine the stability and properties of interfaces of low-index Au surfaces adhered to TiO2(110), using density functional theory energy density calculations. We consider Au(100) and Au(111) epitaxies on rutile TiO2(110) surface, as observed in experiments. For each epitaxy, we consider several different interfaces: Au(111)//TiO2(110) and Au(100)//TiO2(110), with and without bridging oxygen, Au(111) on 1x2 added-row TiO2(110) reconstruction, and Au(111) on a proposed 1x2 TiO reconstruction. The density functional theory energy density method computes the energy changes on each of the atoms while forming the interface, and evaluates the work of adhesion to determine the equilibrium interfacial structure.Comment: 20 pages, 11 figure

Progress in development of a new luminescence setup at the FinEstBeAMS beamline of the MAX IV laboratory

The main funding for the FinEstBeAMS beamline has been obtained from the European Union through the European Regional Development Fund (project “Estonian beamline to MAX-IV synchrotron”, granted to the University of Tartu) and from the Academy of Finland through the Finnish Research Infrastructure funding projects ( FIRI2010 , FIRI2013 , FIRI2014 ). The authors also acknowledge the funding contributions of the University of Oulu , University of Turku , Tampere University of Technology , the Estonian Research Council ( IUT 2-25 , IUT 2-26 , PRG-111 ), as well as the Estonian Centre of Excellence in Research “Advanced materials and high-technology devices for sustainable energetics, sensorics and nanoelectronics” TK141 (2014-2020.4.01.15-0011). The strategic funding of Finnish FIMAX consortium coordinating university , University of Oulu , for beamline personnel is also acknowledged. The authors thank the MAX IV Laboratory for financial and infrastructural support as well as for assistance during the construction of the FinEstBeaMS beamline.FinEstBeAMS is a new materials science beamline at the 1.5 GeV storage ring of the MAX IV Laboratory in Lund, Sweden. It has been built based on grazing incidence monochromatization of synchrotron light, which allows to cover a remarkably wide excitation energy range from ultraviolet to soft x-rays (4.5–1450 eV). A new mobile luminescence spectroscopy end station has been commissioned with design benefitting from the advantages of a high flux elliptically polarizing undulator light source. We report on the design of the luminescence end station, its technical realization and performance achieved so far. Special attention is paid to the experimental challenges for luminescence spectroscopy under grazing incidence excitation conditions. The first luminescence results obtained demonstrate a reliable performance of the advanced setup at FinEstBeAMS.Eesti Teadusagentuur IUT 2-25,PRG-111,IUT 2-26; European Commission; University of Tartu; Academy of Finland FIRI2010,FIRI2013,FIRI2014; Tampereen Teknillinen Yliopisto; Turun Yliopisto; European Regional Development Fund; Institute of Solid State Physics, University of Latvia as the Center of Excellence has received funding from the European Union’s Horizon 2020 Framework Programme H2020-WIDESPREAD-01-2016-2017-TeamingPhase2 under grant agreement No. 739508, project CAMART

Hydride Formation in Single Palladium and Magnesium Nanoparticles Studied By Nanoplasmonic Dark-Field Scattering Spectroscopy

Scrutinizing functional nanosystems and relating details in their size, chemistry, and geometry to functionality remains a significant experimental challenge. Following the concept of indirect nanoplasmonic sensing (INPS), the exploitation of truncated Au nanocones with functionalized tips, nanofabricated in a one step, are used as single nanoplasmonic sensors for dark-field scattering spectroscopy measurements of the hydride formation Au in single Pd and Mg nanoparticles

Grain orientation dependent Nb-Ti microalloying mediated surface segregation on ferritic stainless steel

Surface segregation and oxide formation anisotropy on Ti-Nb stabilized ferritic stainless steel (EN 1.4521) were studied by XPS and Electron Backscatter Diffraction. Competitive surface segregation of Si, Nb and Ti was initiated at ∼550. °C, and segregation was favored to the open surface sites of 〈111〉 oriented grains. Furthermore, the surface segregation of Cr was strongly limited at the locations of stable Ti(CN)- and (NbTi)C-type precipitates. Consequently, the oxidation resistance of stainless steels can be enhanced cost-efficiently, without alloy additions, by optimizing the microstructure to facilitate the fast and uniform growth of protective oxide scale.acceptedVersionPeer reviewe