Solvent effects on the magnetic-field-dependent reaction yields of photogenerated radical ion pairs.

A pronounced solvent viscosity and polarity dependence of the magnetic field effect was found for polymethylene-linked radical ion pairs generated by photoinduced intramolecular electron transfer in compounds of the type pyrene-(CH2)n-N,N-dimethylaniline, with n = 7–16. This is interpreted in terms of the general radical pair mechanism, i.e. the nuclear hyperfine interaction mechanism including a spin-exchange interaction, modulated by the stochastic folding motion of the linking CH2 chain which leads to a “motional deformation” of the reaction yield spectra

Epidemiological observations on pastern dermatitis in young horses and evaluation of essential fatty acid spot-on applications with or without phytosphingosine as prophylactic treatment

Background - Equine pastern dermatitis (EPD) is a common multifactorial clinical syndrome in horses. Treatment can be difficult;pathogenesis and triggering factors cannot always be determined. Objectives - To assess risk factors for developing EPD in a large group of horses kept under the same conditions and to analyse whether or not a spot-on containing essential fatty acids and antimicrobial agents is able to prevent the development of EPD or accelerate the healing process. Animals - Each year 50 young, privately owned, warmblood horses were prospectively included. Methods - All horses were examined weekly between August and October for the presence of typical EPD skin lesions. Additionally, in the first year, horses were randomly divided into three subgroups of intervention. The pastern areas were treated once weekly either with 0.6 mL of a spot-on containing essential fatty acids and aromatic oils, or a preparation containing additional antibacterial phytosphingosine, or not at all. Results - Nonpigmented pastern areas were affected significantly more often than pigmented pastern areas (P < 0.0001). The interaction between moisture and opportunistic pathogens seemed to be a major triggering factor for EPD. There was no difference in the occurrence of EPD in the three subgroups. The lesion scores of affected limbs in both spot-on groups were significantly lower compared to the control group. Conclusion and clinical importance - Moisture and lack of pigmentation predisposed to EPD. Topical application of the tested spot-on once weekly did not prevent the disease. A positive effect of both spot-on products on the severity of EPD lesions was detected

Finite size effects on transport coefficients for models of atomic wires coupled to phonons

We consider models of quasi-1-d, planar atomic wires consisting of several, laterally coupled rows of atoms, with mutually non-interacting electrons. This electronic wire system is coupled to phonons, corresponding, e.g., to some substrate. We aim at computing diffusion coefficients in dependence on the wire widths and the lateral coupling. To this end we firstly construct a numerically manageable linear collision term for the dynamics of the electronic occupation numbers by following a certain projection operator approach. By means of this collision term we set up a linear Boltzmann equation. A formula for extracting diffusion coefficients from such Boltzmann equations is given. We find in the regime of a few atomic rows and intermediate lateral coupling a significant and non-trivial dependence of the diffusion coefficient on both, the width and the lateral coupling. These results, in principle, suggest the possible applicability of such atomic wires as electronic devices, such as, e.g., switches.Comment: 9 pages, 5 figures, accepted for publication in Eur. Phys. J.

Transition of Molecule Orientation during Adsorption of Terephthalic Acid on Rutile TiO2(110)

Rahe P, Nimmrich M, Nefedov A, Naboka M, Wöll C, Kühnle A. Transition of Molecule Orientation during Adsorption of Terephthalic Acid on Rutile TiO2(110). Journal of Physical Chemistry C. 2009;113(40):17471-17478.The coverage-dependent mode of adsorption of terephthalic acid [C6H4(COOH)(2), TPA] on rutile TiO2(110) was investigated by means of noncontact atomic force microscopy (NC-AFM) and near-edge X-ray absorption fine structure (NEXAFS) spectroscopy under ultrahigh vacuum conditions at room temperature. Individual molecules are observed to adsorb in an disordered, flat-lying geometry at low coverages up to similar to 0.3 monolayer (ML). The molecules are immobile at room temperature. implying a diffusion barrier larger than 0.8 eV. This rather high value might be explained by anchoring to surface defect sites. A transition from flat-lying to upright-oriented molecules is revealed by NEXAFS when saturation coverage is achieved. High-resolution NC-AFM images reveal two different Structures at coverages between similar to 0.8 and 1 ML: (i) a well-ordered (2 x 1) structure and (ii) a structure of single and paired rows oriented along the [001] crystallographic direction. The latter structure might originate from a pairwise interaction of two neighboring molecules through the top carboxyl groups. Further increase in the exposure results in it saturation of the corresponding signal in the NEXAFS spectra, revealing that the growth of TPA oil TiO2(110) at room temperature is self-limiting

Generic nature of long-range repulsion mechanism on a bulk insulator?

Neff JL, Richter A, Söngen H, et al. Generic nature of long-range repulsion mechanism on a bulk insulator? Faraday Discussions. 2017;204:419-428

Smooth crack-free targets for nuclear applications produced by molecular plating

Vascon A, Santi S, Isse AA, et al. Smooth crack-free targets for nuclear applications produced by molecular plating. Nuclear Instruments and Methods in Physics Research A. 2013;714:163-175.The production process of smooth and crack-free targets by means of constant current electrolysis in organic media, commonly known as molecular plating, was optimized. Using a Nd salt, i.e., [Nd(NO3)(3)center dot 6H(2)O], as model electrolyte several constant current density electrolysis experiments were carried out to investigate the effects of different parameters, namely the plating solvent (isopropanol and isobutanol mixed together, pyridine, and N,N-dimethylformamide), the electrolyte concentration (0.11, 0.22, 0.44 mM), the applied current density (0.17, 0.3, 0.7, and 1.3 mA/cm(2)), and the surface roughness of the deposition substrates (12 and 24 nm). Different environments (air and Ar) were used to dry the samples and the effects on the produced layers were investigated. The obtained deposits were characterized using gamma-ray spectroscopy for determining Nd deposition yields, X-ray photoelectron spectroscopy for chemical analysis of the produced surfaces, radiographic imaging for surface homogeneity inspection, atomic force microscopy for surface roughness evaluation, and scanning electron microscopy for surface morphology investigation. The results allowed identifying the optimum parameters for the production of smooth and crack-free targets by means of molecular plating. The smoothest layers, which had an average RMS roughness of ca. 20 nm and showed no cracks, were obtained using 0.22 mM [Nd(NO3)(3)center dot 6H(2)O] plated from N,N-dimethylformamide at current densities in the range of 0.3-0.7 mA/cm(2) on the smoothest deposition substrate available. (c) 2013 Elsevier B.V. All rights reserved

Diacetylene polymerization on a bulk insulator surface

Richter A, Haapasilta V, Venturini C, et al. Diacetylene polymerization on a bulk insulator surface. Physical Chemistry Chemical Physics. 2017;19(23):15172-15176.Molecular electronics has great potential to surpass known limitations in conventional silicon-based technologies. The development of molecular electronics devices requires reliable strategies for connecting functional molecules by wire-like structures. To this end, diacetylene polymerization has been discussed as a very promising approach for contacting single molecules with a conductive polymer chain. A major challenge for future device fabrication is transferring this method to bulk insulator surfaces, which are mandatory to decouple the electronic structure of the functional molecules from the support surface. Here, we provide experimental evidence for diacetylene polymerization of 3,30-(1,3-butadiyne-1,4-diyl) bisbenzoic acid precursors on the (10.4) surface of calcite, a bulk insulator with a band gap of around 6 eV. When deposited on the surface held at room temperature, ordered islands with a (1 x 3) superstructure are observed using dynamic atomic force microscopy. A distinct change is revealed upon heating the substrate to 485 K. After heating, molecular stripes with a characteristic inner structure are formed that excellently match the expected diacetylene polymer chains in appearance and repeat distance. The corresponding density functional theory computations reveal molecular-level bonding patterns of both the (1 x 3) superstructure and the formed striped structure, confirming the assignment of on-surface diacetylene polymerization. Transferring the concept of using diacetylene polymerization for creating conductive connections to bulk insulator surfaces paves the way towards application-relevant systems for future molecular electronic devices

Gravitational stability of suspensions of attractive colloidal particles

Kim C, Liu Y, Kühnle A, et al. Gravitational stability of suspensions of attractive colloidal particles. Physical Review Letters. 2007;99(2):028303.Colloidal suspensions are susceptible to gravitationally induced phase separation. This can be mitigated by the formation of a particle network caused by depletion attraction. The effectiveness of this network in supporting the buoyant weight of the suspension can be characterized by its compressional modulus. We measure the compressional modulus for emulsion networks induced by depletion attraction and present a model that quantitatively predicts their gravitational stability. We also determine the relationship between the strength of the depletion attraction and the magnitude of the compressional modulus

Structure-Dependent Dissolution and Restructuring of Calcite Surfaces by Organophosphonates

Nalbach M, Moschona A, Demadis KD, Klassen S, Bechstein R, Kühnle A. Structure-Dependent Dissolution and Restructuring of Calcite Surfaces by Organophosphonates. Crystal Growth &amp; Design. 2017;17(11):5867-5874

Atomic-resolution imaging of clean and hydrogen-terminated C(100)-(2x1) diamond surfaces using noncontact AFM

Nimmrich M, Kittelmann M, Rahe P, et al. Atomic-resolution imaging of clean and hydrogen-terminated C(100)-(2x1) diamond surfaces using noncontact AFM. Physical Review B. 2010;81(20): 201403.High-purity, type IIa diamond is investigated by noncontact atomic force microscopy (NC-AFM). We present atomic-resolution images of both the electrically conducting hydrogen-terminated C(100)-(2 x 1) : H surface and the insulating C(100)-(2 x 1) surface. For the hydrogen-terminated surface, a nearly square unit cell is imaged. In contrast to previous scanning tunneling microscopy experiments, NC-AFM imaging allows both hydrogen atoms within the unit cell to be resolved individually, indicating a symmetric dimer alignment. Upon removing the surface hydrogen, the diamond sample becomes insulating. We present atomic-resolution images, revealing individual C-C dimers. Our results provide real-space experimental evidence for a (2 x 1) dimer reconstruction of the truly insulating C(100) surface