Imaging spin-reorientation transitions in consecutive atomic Co layers on Ru(0001)

By means of spin-polarized low-energy electron microscopy, we show that the magnetic easy axis of one to three atomic-layer thick cobalt films on Ru(0001) changes its orientation twice during deposition: One-monolayer and three-monolayer thick films are magnetized in plane, while two-monolayer films are magnetized out of plane. The Curie temperatures of films thicker than one monolayer are well above room temperature. Fully relativistic calculations based on the screened Korringa-Kohn-Rostoker method demonstrate that only for two-monolayer cobalt films does the interplay between strain, surface, and interface effects lead to perpendicular magnetization.     

A mass spectrometric line for tritium analysis of water and noble gas measurements from different water amounts in the range of microlitres and millilitres

This paper describes the procedure followed for noble gas measurements for litres, millilitres and microlitres of water samples in our laboratory, including sample preparation, mass spectrometric measurement procedure, and the complete calibrations. The preparation line extracts dissolved gases from water samples of volumes of 0.2 μ l to 3 l and it separates them as noble and other chemically active gases. Our compact system handles the following measurements: (i) determination of tritium concentration of environmental water samples by the ³He ingrowth method; (ii) noble gas measurements from surface water and groundwater; and (iii) noble gas measurements from fluid inclusions of solid geological archives (e.g. speleothems). As a result, the tritium measurements have a detection limit of 0.012 TU, and the expectation value (between 1 and 20 TU) is within 0.2 % of the real concentrations with a standard deviation of 2.4 %. The reproducibility of noble gas measurements for water samples of 20–40 ml allows us to determine solubility temperatures by an uncertainty better than 0.5 °C. Moreover, noble gas measurements for tiny water amounts (in the microlitre range) show that the results of the performed calibration measurements for most noble gas isotopes occur with a deviation of less than 2 %. Theoretically, these precisions for noble gas concentrations obtained from measurements of waters samples of a few microlitres allow us to determine noble gas temperatures by an uncertainty of less than 1 °C. Here, we present the first noble gas measurements of tiny amounts of artificial water samples prepared under laboratory conditions.     

Adaptive Neuro-Fuzzy Inference System and a Multilayer Perceptron Model Trained with Grey Wolf Optimizer for Predicting Solar Diffuse Fraction

The accurate prediction of the solar diffuse fraction (DF), sometimes called the diffuse ratio, is an important topic for solar energy research. In the present study, the current state of Diffuse irradiance research is discussed and then three robust, machine learning (ML) models are examined using a large dataset (almost eight years) of hourly readings from Almeria, Spain. The ML models used herein, are a hybrid adaptive network-based fuzzy inference system (ANFIS), a single multi-layer perceptron (MLP) and a hybrid multi-layer perceptron grey wolf optimizer (MLP-GWO). These models were evaluated for their predictive precision, using various solar and DF irradiance data, from Spain. The results were then evaluated using frequently used evaluation criteria, the mean absolute error (MAE), mean error (ME) and the root mean square error (RMSE). The results showed that the MLP-GWO model, followed by the ANFIS model, provided a higher performance in both the training and the testing procedures.     

Probing the potential of N-heterocyclic carbenes in molecular electronics: redox-active metal centers interlinked by a rigid ditopic carbene ligand

Bimetallic homonuclear iron(II) and ruthenium(II) N-heterocyclic carbene complexes have been synthesized and crystallographically analyzed. As a spacer ligand for interconnecting the two redox-active metal centers, a ditopic carbene ligand has been used that comprises two carbene sites annelated to benzene. Detailed electrochemical and spectroelectrochemical analyses of the bimetallic systems revealed that despite the potentially pi-delocalized nature of the ditopic ligand, the iron centers are only moderately coupled. In the ruthenium complexes, the intermetallic interactions are very weak and the centers are electrochemically nearly independent. A model is proposed for rationalizing these observations which is based on (I) relatively weak charge delocalization in the spacer ligand and (II) on electrostatic factors governing the metal-carbene bond.     

C-H bond activation of coordinated pyridine: ortho-pyridyl-ditechnetiumhydridocarbonyl metal cyclus. Crystal structure and dynamic behavior in solution

The reaction of pyridine with ditechnetium decacarbonyl [Tc2(CO)10] (1) leads to a novel ortho-pyridyl-ditechnetium hydrido complex, [Tc2(mu-H)(mu-NC5H4)(NC5H5)2(CO)6] (2) and its precursor [Tc2(mu-CO)2(NC5H5)2(CO)6] (3). At ambient temperature 1 was found to react slowly with pyridine to afford the substitution product 3 after 120 h. However, heating the reaction mixture to reflux exclusively leads to the pyridine-ortho-metalated complex 2 in only 30 min. Similarly, complex 3 can be converted completely into 2 upon heating in pyridine for 30 min. Both compounds 2 and 3 were characterized by NMR spectroscopy and X-ray analysis. Both compounds 2 and 3 show a complex dynamic behavior in solution that was investigated by one-dimensional and two-dimensional NMR spectroscopy. Both compounds 2 and 3 show isomerization in solution according to the relative position of the non-bridging pyridine ligands. For 2 the existence of three isomers was shown at equilibrium conditions, 2a (56%) with trans-diaxial, 2b (38%) with cis-diaxial, and 2c (6%) with axial-equatorial arrangement of the non-bridging pyridines. For 3 an equilibrium was detected between two isomers, 3a (67%) with a cis-diaxial and 3b (33%) with a trans-diaxial arrangement of the pyridines.