Control of the Stability, Electron-Transfer Kinetics, and pH-Dependent Energetics of Si/H_2O Interfaces through Methyl Termination of Si(111) Surfaces

Methyl-terminated, n-type, (111)-oriented Si surfaces were prepared via a two-step chlorination-alkylation method. This surface modification passivated the Si surface toward electrochemical oxidation and thereby allowed measurements of interfacial electron-transfer processes in contact with aqueous solutions. The resulting semiconductor/liquid junctions exhibited interfacial kinetics behavior in accord with the ideal model of a semiconductor/liquid junction. In contrast to the behavior of H-terminated Si(111) surfaces, current density vs. potential measurements of CH_3-terminated Si(111) surfaces in contact with an electron acceptor having a pH-independent redox potential (methyl viologen^(2+/+)) were used to verify that the band edges of the modified Si electrode were fixed with respect to changes in solution pH. The results provide strong evidence that the energetics of chemically modified Si interfaces can be fixed with respect to pH and show that the band-edge energies of Si can be tuned independently of pH-derived variations in the electrochemical potential of the solution redox species

Ab initio Molecular Dynamics in Adaptive Coordinates

We present a new formulation of ab initio molecular dynamics which exploits the efficiency of plane waves in adaptive curvilinear coordinates, and thus provides an accurate treatment of first-row elements. The method is used to perform a molecular dynamics simulation of the CO_2 molecule, and allows to reproduce detailed features of its vibrational spectrum such as the splitting of the Raman sigma+_g mode caused by Fermi resonance. This new approach opens the way to highly accurate ab initio simulations of organic compounds.Comment: 11 pages, 3 PostScript figure

Measurement of the Free-Energy Dependence of Interfacial Charge-Transfer Rate Constants using ZnO/H_2O Semiconductor/Liquid Contacts

The dependence of electron-transfer rate constants on the driving force for interfacial charge transfer has been investigated using n-type ZnO electrodes in aqueous solutions. Differential capacitance versus potential and current density versus potential measurements were used to determine the energetics and kinetics, respectively, of the interfacial electron-transfer processes. A series of nonadsorbing, one-electron, outer-sphere redox couples with formal reduction potentials that spanned approximately 900 mV allowed evaluation of both the normal and Marcus inverted regions of interfacial electron-transfer processes. All rate processes were observed to be kinetically first-order in the concentration of surface electrons and first-order in the concentration of dissolved redox acceptors. The band-edge positions of the ZnO were essentially independent of the Nernstian potential of the solution over the range 0.106−1.001 V vs SCE. The rate constant at optimal exoergicity was observed to be approximately 10^(-16) cm4 s^(-1). The rate constant versus driving force dependence at n-type ZnO electrodes exhibited both normal and inverted regions, and the data were well-fit by a parabola generated using classical Marcus theory with a reorganization energy of 0.67 eV. NMR line broadening measurements of the self-exchange rate constants indicated that the redox couples had reorganization energies of 0.64−0.69 eV. The agreement between the reorganization energy of the ions in solution and the reorganization energy for the interfacial electron-transfer processes indicated that the reorganization energy was dominated by the redox species in the electrolyte, as expected from an application of Marcus theory to semiconductor electrodes

Cosmological parameters constraints from galaxy cluster mass function measurements in combination with other cosmological data

We present the cosmological parameters constraints obtained from the combination of galaxy cluster mass function measurements (Vikhlinin et al., 2009a,b) with new cosmological data obtained during last three years: updated measurements of cosmic microwave background anisotropy with Wilkinson Microwave Anisotropy Probe (WMAP) observatory, and at smaller angular scales with South Pole Telescope (SPT), new Hubble constant measurements, baryon acoustic oscillations and supernovae Type Ia observations. New constraints on total neutrino mass and effective number of neutrino species are obtained. In models with free number of massive neutrinos the constraints on these parameters are notably less strong, and all considered cosmological data are consistent with non-zero total neutrino mass \Sigma m_\nu \approx 0.4 eV and larger than standard effective number of neutrino species, N_eff \approx 4. These constraints are compared to the results of neutrino oscillations searches at short baselines. The updated dark energy equation of state parameters constraints are presented. We show that taking in account systematic uncertainties, current cluster mass function data provide similarly powerful constraints on dark energy equation of state, as compared to the constraints from supernovae Type Ia observations.Comment: Accepted for publication in Astronomy Letter

Theoretical investigation of carbon defects and diffusion in α-quartz

The geometries, formation energies, and diffusion barriers of carbon point defects in silica (α-quartz) have been calculated using a charge-self-consistent density-functional based nonorthogonal tight-binding method. It is found that bonded interstitial carbon configurations have significantly lower formation energies (on the order of 5 eV) than substitutionals. The activation energy of atomic C diffusion via trapping and detrapping in interstitial positions is about 2.7 eV. Extraction of a CO molecule requires an activation energy <3.1 eV but the CO molecule can diffuse with an activation energy <0.4 eV. Retrapping in oxygen vacancies is hindered—unlike for O2—by a barrier of about 2 eV

A 2.3-Day Periodic Variability in the Apparently Single Wolf-Rayet Star WR 134: Collapsed Companion or Rotational Modulation?

We present the results of an intensive campaign of spectroscopic and photometric monitoring of the peculiar Wolf-Rayet star WR 134 from 1989 to 1997. This unprecedentedly large data set allows us to confirm unambiguously the existence of a coherent 2.25 +/- 0.05 day periodicity in the line-profile changes of He II 4686, although the global pattern of variability is different from one epoch to another. This period is only marginally detected in the photometric data set. Assuming the 2.25 day periodic variability to be induced by orbital motion of a collapsed companion, we develop a simple model aiming at investigating (i) the effect of this strongly ionizing, accreting companion on the Wolf-Rayet wind structure, and (ii) the expected emergent X-ray luminosity. We argue that the predicted and observed X-ray fluxes can only be matched if the accretion on the collapsed star is significantly inhibited. Additionally, we performed simulations of line-profile variations caused by the orbital revolution of a localized, strongly ionized wind cavity surrounding the X-ray source. A reasonable fit is achieved between the observed and modeled phase-dependent line profiles of He II 4686. However, the derived size of the photoionized zone substantially exceeds our expectations, given the observed low-level X-ray flux. Alternatively, we explore rotational modulation of a persistent, largely anisotropic outflow as the origin of the observed cyclical variability. Although qualitative, this hypothesis leads to greater consistency with the observations.Comment: 34 pages, 16 figures. Accepted by the Astrophysical Journa

Water oxidation at hematite photoelectrodes: the role of surface states

Hematite (α-Fe2O3) constitutes one of the most promising semiconductor materials for the conversion of sunlight into chemical fuels by water splitting. Its inherent drawbacks related to the long penetration depth of light and poor charge carrier conductivity are being progressively overcome by employing nanostructuring strategies and improved catalysts. However, the physical–chemical mechanisms responsible for the photoelectrochemical performance of this material (J(V) response) are still poorly understood. In the present study we prepared thin film hematite electrodes by atomic layer deposition to study the photoelectrochemical properties of this material under water-splitting conditions. We employed impedance spectroscopy to determine the main steps involved in photocurrent production at different conditions of voltage, light intensity, and electrolyte pH. A general physical model is proposed, which includes the existence of a surface state at the semiconductor/liquid interface where holes accumulate. The strong correlation between the charging of this state with the charge transfer resistance and the photocurrent onset provides new evidence of the accumulation of holes in surface states at the semiconductor/electrolyte interface, which are responsible for water oxidation. The charging of this surface state under illumination is also related to the shift of the measured flat-band potential. These findings demonstrate the utility of impedance spectroscopy in investigations of hematite electrodes to provide key parameters of photoelectrodes with a relatively simple measurement

Constructing living buildings: a review of relevant technologies for a novel application of biohybrid robotics

Biohybrid robotics takes an engineering approach to the expansion and exploitation of biological behaviours for application to automated tasks. Here, we identify the construction of living buildings and infrastructure as a high-potential application domain for biohybrid robotics, and review technological advances relevant to its future development. Construction, civil infrastructure maintenance and building occupancy in the last decades have comprised a major portion of economic production, energy consumption and carbon emissions. Integrating biological organisms into automated construction tasks and permanent building components therefore has high potential for impact. Live materials can provide several advantages over standard synthetic construction materials, including self-repair of damage, increase rather than degradation of structural performance over time, resilience to corrosive environments, support of biodiversity, and mitigation of urban heat islands. Here, we review relevant technologies, which are currently disparate. They span robotics, self-organizing systems, artificial life, construction automation, structural engineering, architecture, bioengineering, biomaterials, and molecular and cellular biology. In these disciplines, developments relevant to biohybrid construction and living buildings are in the early stages, and typically are not exchanged between disciplines. We, therefore, consider this review useful to the future development of biohybrid engineering for this highly interdisciplinary application.publishe