Searching the Chemical Space of Bicyclic Dienes for Molecular Solar Thermal Energy Storage Candidates

Photoswitches are molecular systems that are chemically transformed subsequent to interaction with light and they find potential application in many new technologies. The design and discovery of photoswitch candidates require intricate molecular engineering of a range of properties to optimize a candidate to a specific applications, a task which can be tackled efficiently using quantum chemical screening procedures. In this paper, we perform a large scale screening of approximately half a million bicyclic diene photoswitches in the context of molecular solar thermal energy storage using ab initio quantum chemical methods. We further device an efficient strategy for scoring the systems based on their predicted solar energy conversion efficiency and elucidate potential pitfalls of this approach. Our search through the chemical space of bicyclic dienes reveals systems with unprecedented solar energy conversion efficiencies and storage densities that show promising design guidelines for next generation molecular solar thermal energy storage systems.     

Surface structure and morphology of InAs(1 1 1)B with/without gold nanoparticles annealed under arsenic or atomic hydrogen flux

We have investigated the structure and morphology of the InAs(1 1 1)B surface using Low Energy Electron Diffraction (LEED), Scanning Tunneling Microscopy (STM) and Scanning Electron Microscopy (SEM). The surface was prepared by annealing in the presence of an arsenic or atomic hydrogen pressure. A (2 × 2) reconstruction that changes into a (1 × 1) unreconstructed surface after prolonged annealing was observed irrespective of preparation method, while the surface morphology was distinctly different in the two cases. Detailed atomic scale models are proposed to explain the behavior. Deposition of Au aerosol nanoparticles on the sample prior to annealing was found to have no effect on the surface reconstruction. The Au particles were found to sink into the surface.     

A cyclic dinucleotide with a four-carbon 5'-C-to-5'-C connection; synthesis by RCM, NMR-examination and incorporation into secondary nucleic acid structures

A 5'-C-allylthymidine derivative was prepared from thymidine by the application of a stereoselective allylation procedure and its 5'(S)-configuration was confirmed. From this nucleoside derivative, appropriately protected building blocks were prepared and coupled using standard phosphoramidite chemistry to afford a dinucleotide with two 5'-C-allylgroups. This molecule was used as a substrate for a ring-closing metathesis (RCM) reaction and after deprotection, a 1 : 1 mixture of E- and Z-isomers of a cyclic dinucleotide with an unsaturated 5'-C-to-5'-C connection was obtained. Alternatively, a hydrogenation of the double bond and deprotection afforded a saturated cyclic dinucleotide. An advanced NMR-examination confirmed the constitution of this molecule and indicated a restriction in its overall conformational freedom. After variation of the protecting group strategy, a phosphoramidite building block of the saturated cyclic dinucleotide with the 5'-O-position protected as a pixyl ether and the phosphate protected as a methyl phosphotriester was obtained. This building block was used in the preparation of two 14-mer oligonucleotides with a central artificial bend due to the cyclic dinucleotide moiety. These were found to destabilise duplexes, slightly destabilise bulged duplexes but, to some extent, stabilise a three-way junction in high Mg(2+)-concentrations.     

Competitive clustering in a bidisperse granular gas

A bidisperse granular gas in a compartmentalized system is experimentally found to cluster competitively: Depending on the shaking strength, the clustering can be directed either towards the compartment initially containing mainly small particles or to the one containing mainly large particles. The experimental observations are quantitatively explained within a flux model.     

Automatic gain control of semiconductor laser amplifiers

A new approach to automatic gain control has been demonstrated and a signal polarization independent operation over a 35-nm wavelength range at a gain level of 17 dB has been obtained.     

Experimental evidence for a partially dissociated water bilayer on Ru[0001

Core-level photoelectron spectra, in excellent agreement with ab initio calculations, confirm that the stable wetting layer of water on Ru[0001] contains O-H and H2O in roughly 3:5 proportion, for OHx coverages between 0.25 and 0.7 ML, and T<170 K. Proton disorder explains why the wetting structure looks to low energy electron diffraction (LEED) to be an ordered p(square root of 3 x square root of 3)R30 degrees adlayer, even though approximately 3/8 of its molecules are dissociated. Complete dissociation to atomic oxygen starts near 190 K. Low photon flux in the synchrotron experiments ensured that the diagnosis of the nature of the wetting structure quantified by LEED is free of beam-induced damage.     

Density of configurational states from first-principles calculations: the phase diagram of Al-Na surface alloys.

The structural phases of Al(x)Na(1-x) surface alloys have been investigated theoretically and experimentally. We describe the system using a lattice-gas Hamiltonian, determined from density functional theory, together with Monte Carlo (MC) calculations. The obtained phase diagram reproduces the experiment on a quantitative level. From calculation of the (configurational) density of states by the recently introduced Wang-Landau MC algorithm, we derive thermodynamic quantities, such as the free energy and entropy, which are not directly accessible from conventional MC simulations. We accurately reproduce the stoichiometry, as well as the temperature at which an order-disorder phase transition occurs, and demonstrate the crucial role, and magnitude, of the configurational entropy.     

Novel instrument for high temperature thermogravimetric measurements in high water vapour contents

Summary A novel instrument for high temperature thermogravimetric measurements in atmospheres containing high water vapour contents was developed in a collaboration between Netzsch and Risø National Laboratory. The development of the instrument was initiated to facilitate the investigation of high temperature corrosion of steels in humidified atmospheres. The instrument consists of a standard thermal analyser unit, including a new water vapour furnace, balance and sample carrier. The design of the instrument is discussed and thermogravimetric measurements on a Fe₇₈Cr₂₂ steel are presented.     

Singlet Sigma: The "Other" Singlet Oxygen in Solution

The lowest excited electronic state of molecular oxygen, O₂(a^1-DL_g), is often called simply singlet oxygen. This singlet delta state is an acknowledged and well-studied intermediate in many solution-phase photosystems. However, the second excited electronic state of oxygen, O₂(b¹δ_g+), is also a singlet. It has recently become possible to monitor this singlet sigma state in solution, which, in combination with studies of the singlet delta state, contributes to a better understanding of a variety of general problems in chemistry.     

Flow diagnostics downstream of a tribladed rotor model

This paper presents results of a study of vortex wake structures and measurements of instantaneous 3D velocity fields downstream of a triblade turbine model. Two operation modes of flow around the rotor with different tip speed ratios were tested. Initially the wake structures were visualized and subsequently quantitative data were recorded through velocity field restoration from particle tracks using a stereo PIV system. The study supplied flow diagnostics and recovered the instantaneous 3D velocity fields in the longitudinal cross section behind a tribladed rotor at different values of tip speed ratio. This set of data provided a basis for testing and validating assumptions and hypothesis regarding classical theories of rotors.