Tuning the structural and magnetic properties of Sr 2 FeReO 6 by substituting Fe and Re with valence invariant metals

In the course of this work the effect of metal substitution on the structural and magnetic properties of the double perovskites Sr2MM’O6 (M = Fe, substituted by Cr, Zn and Ga; M’ = Re, substituted by Sb) was explored by means of X-ray diffraction, magnetic measurements, band structure calculations, Mößbauer spectroscopy and conductivity measurements. The focus of this study was the determination of (i) the kind and structural boundary conditions of the magnetic interaction between the M and M’ cations and (ii) the conditions for the principal application of double perovskites as spintronic materials by means of the band model approach. Strong correlations between the electronic, structural and magnetic properties have been found during the study of the double perovskites Sr2Fe1-xMxReO6 (0 < x < 1, M = Zn, Cr). The interplay between van Hove-singularity and Fermi level plays a crucial role for the magnetic properties. Substitution of Fe by Cr in Sr2FeReO6 leads to a non-monotonic behaviour of the saturation magnetization (MS) and an enhancement for substitution levels up to 10 %. The Curie temperatures (TC) monotonically increase from 401 to 616 K. In contrast, Zn substitution leads to a continuous decrease of MS and TC. The diamagnetic dilution of the Fe-sublattice by Zn leads to a transition from an itinerant ferrimagnetic to a localized ferromagnetic material. Thus, Zn substitution inhibits the long-range ferromagnetic interaction within the Fe-sublattice and preserves the long-range ferromagnetic interaction within the Re-sublattice. Superimposed on the electronic effects is the structural influence which can be explained by size effects modelled by the tolerance factor t. In the case of Cr substitution, a tetragonal – cubic transformation for x > 0.4 is observed. For Zn substituted samples the tetragonal distortion linearly increases with increasing Zn content. In order to elucidate the nature of the magnetic interaction between the M and M’ cations, Fe and Re were substituted by the valence invariant main group metals Ga and Sb, respectively. X-ray diffraction reveals Sr2FeRe1-xSbxO6 (0 < x < 0.9) to crystallize without antisite disorder in the tetragonal distorted perovskite structure (space group I4/mmm). The ferrimagnetic behaviour of the parent compound Sr2FeReO6 changes to antiferromagnetic upon Sb substitution as determined by magnetic susceptibility measurements. Samples up to a doping level of 0.3 are ferrimagnetic, while Sb contents higher than 0.6 result in an overall antiferromagnetic behaviour. 57Fe Mößbauer results show a coexistence of ferri- and antiferromagnetic clusters within the same perovskite-type crystal structure in the Sb substitution range 0.3 < x < 0.8, whereas Sr2FeReO6 and Sr2FeRe0.9Sb0.1O6 are “purely” ferrimagnetic and Sr2FeRe0.1Sb0.9O6 contains antiferromagnetically ordered Fe sites only. Consequently, a replacement of the Re atoms by a nonmagnetic main group element such as Sb blocks the double exchange pathways Fe–O–Re(Sb)–O–Fe along the crystallographic axis of the perovskite unit cell and destroys the itinerant magnetism of the parent compound. The structural and magnetic characterization of Sr2Fe1-xGaxReO6 (0 < x < 0.7) exhibit a Ga/Re antisite disorder which is unexpected because the parent compound Sr2FeReO6 shows no Fe/Re antisite disorder. This antisite disorder strongly depends on the Ga content of the sample. Although the X-ray data do not hint at a phase separation, sample inhomogeneities caused by a demixing are observed by a combination of magnetic characterization and Mößbauer spectroscopy. The 57Fe Mößbauer data suggest the formation of two types of clusters, ferrimagnetic Fe- and paramagnetic Ga-based ones. Below 20 % Ga content, Ga statistically dilutes the Fe–O–Re–O–Fe double exchange pathways. Cluster formation begins at x = 0.2, for 0.2 < x < 0.4 the paramagnetic Ga-based clusters do not contain any Fe. Fe containing Ga-based clusters which can be detected by Mößbauer spectroscopy firstly appear for x = 0.4.

Measurement of the elastic electron-proton cross section and separation of the electric and magnetic form factor in the Q 2 range from 0.004 to 1 (GeV/c) 2

The electromagnetic form factors of the proton are fundamental quantities sensitive to the distribution of charge and magnetization inside the proton. Precise knowledge of the form factors, in particular of the charge and magnetization radii provide strong tests for theory in the non-perturbative regime of QCD. However, the existing data at Q^2 below 1 (GeV/c)^2 are not precise enough for a hard test of theoretical predictions.rnrnFor a more precise determination of the form factors, within this work more than 1400 cross sections of the reaction H(e,e′)p were measured at the Mainz Microtron MAMI using the 3-spectrometer-facility of the A1-collaboration. The data were taken in three periods in the years 2006 and 2007 using beam energies of 180, 315, 450, 585, 720 and 855 MeV. They cover the Q^2 region from 0.004 to 1 (GeV/c)^2 with counting rate uncertainties below 0.2% for most of the data points. The relative luminosity of the measurements was determined using one of the spectrometers as a luminosity monitor. The overlapping acceptances of the measurements maximize the internal redundancy of the data and allow, together with several additions to the standard experimental setup, for tight control of systematic uncertainties.rnTo account for the radiative processes, an event generator was developed and implemented in the simulation package of the analysis software which works without peaking approximation by explicitly calculating the Bethe-Heitler and Born Feynman diagrams for each event.rnTo separate the form factors and to determine the radii, the data were analyzed by fitting a wide selection of form factor models directly to the measured cross sections. These fits also determined the absolute normalization of the different data subsets. The validity of this method was tested with extensive simulations. The results were compared to an extraction via the standard Rosenbluth technique.rnrnThe dip structure in G_E that was seen in the analysis of the previous world data shows up in a modified form. When compared to the standard-dipole form factor as a smooth curve, the extracted G_E exhibits a strong change of the slope around 0.1 (GeV/c)^2, and in the magnetic form factor a dip around 0.2 (GeV/c)^2 is found. This may be taken as indications for a pion cloud. For higher Q^2, the fits yield larger values for G_M than previous measurements, in agreement with form factor ratios from recent precise polarized measurements in the Q2 region up to 0.6 (GeV/c)^2.rnrnThe charge and magnetic rms radii are determined as rn⟨r_e⟩=0.879 ± 0.005(stat.) ± 0.004(syst.) ± 0.002(model) ± 0.004(group) fm,rn⟨r_m⟩=0.777 ± 0.013(stat.) ± 0.009(syst.) ± 0.005(model) ± 0.002(group) fm.rnThis charge radius is significantly larger than theoretical predictions and than the radius of the standard dipole. However, it is in agreement with earlier results measured at the Mainz linear accelerator and with determinations from Hydrogen Lamb shift measurements. The extracted magnetic radius is smaller than previous determinations and than the standard-dipole value.

Reactive halogen compounds in the marine boundary layer: method developments and field measurements

Reactive halogen compounds are known to play an important role in a wide variety of atmospheric processes such as atmospheric oxidation capacity and coastal new particle formation. In this work, novel analytical approaches combining diffusion denuder/impinger sampling techniques with gas chromatographic–mass spectrometric (GC–MS) determination are developed to measure activated chlorine compounds (HOCl and Cl2), activated bromine compounds (HOBr, Br2, BrCl, and BrI), activated iodine compounds (HOI and ICl), and molecular iodine (I2). The denuder/GC–MS methods have been used to field measurements in the marine boundary layer (MBL). High mixing ratios (of the order of 100 ppt) of activated halogen compounds and I2 are observed in the coastal MBL in Ireland, which explains the ozone destruction observed. The emission of I2 is found to correlate inversely with tidal height and correlate positively with the levels of O3 in the surrounding air. In addition the release is found to be dominated by algae species compositions and biomass density, which proves the “hot-spot” hypothesis of atmospheric iodine chemistry. The observations of elevated I2 concentrations substantially support the existence of higher concentrations of littoral iodine oxides and thus the connection to the strong ultra-fine particle formation events in the coastal MBL.

Ein Experiment zur Bestimmung des g-Faktors des gebundenen Elektrons in wasserstoff- und lithiumähnlichen mittelschweren Ionen

In dieser Arbeit werden der experimentelle Aufbau und erste Messungen für die Bestimmung des g-Faktors des Elektrons gebunden in wasserstoff- und lithiumähnlichen mittelschweren Ionen beschrieben. Mit dem hochpräzisenWert des g-Faktors können theoretische Berechnungen der Quantenelektrodynamik gebundener Zustände überprüft werden. Die Messungen werden in einem Dreifach-Penningfallen-System durchgeführt. Dort wurden im Rahmen dieser Arbeit auch erstmals hochgeladene Ionen bis 28Si13+ in einer hierfür entwickelten Elektronenstrahl-Ionenquelle/-falle erzeugt. Für die Bestimmung des g-Faktors werden die freie Zyklotronfrequenz und die Larmorfrequenz benötigt. Erstere wird aus den drei Eigenfrequenzen des in der Präzisionsfalle gespeicherten Ions berechnet. Um das Ion bei den Messungen nicht zu verlieren, werden die Eigenfrequenzen des Ions durch Kopplung an einen radiofrequenten Nachweisschwingkreis nicht-destruktiv nachgewiesen. Die freie Zyklotronfrequenz konnte dabei mit einer relativen Genauigkeit von wenigen 10E−9 bestimmt werden. Zur Bestimmung der Larmorfrequenz ist die genaue Kenntnis der Spinrichtung des Elektrons im Magnetfeld notwendig. Diese wird durch den kontinuierlichen Stern-Gerlach-Effekt in der sogenannten Analysefalle bestimmt. Hierzu muss eine hohe Stabilität der axialen Frequenz des Ions erreicht werden. Um dies sowie die Hochpräzisionsmessungen in der Präzisionsfalle zu erreichen, wurden in dieser Arbeit beide Fallen hinsichtlich ihrer elektrischen und magnetischen Eigenschaften charakterisiert.

Laboratory and field measurements of enantiomeric and non-enantiomeric biogenic VOCs and anthropogenic BTEX compounds

This doctoral thesis was focused on the investigation of enantiomeric and non-enantiomeric biogenic organic compound (BVOC) emissions from both leaf and canopy scales in different environments. In addition, the anthropogenic compounds benzene, toluene, ethylbenzene, and xylenes (BTEX) were studied. BVOCs are emitted into the lower troposphere in large quantities (ca. 1150 Tg C ·yr-1), approximately an order of magnitude greater than the anthropogenic VOCs. BVOCs are particularly important in tropospheric chemistry because of their impact on ozone production and secondary organic aerosol formation or growth. The BVOCs examined in this study were: isoprene, (-)/ (+)-α-pinene, (-)/ (+)-ß-pinene, Δ-3-carene, (-)/ (+)-limonene, myrcene, eucalyptol and camphor, as these were the most abundant BVOCs observed both in the leaf cuvette study and the ambient measurements. In the laboratory cuvette studies, the sensitivity of enantiomeric enrichment change from the leaf emission has been examined as a function of light (0-1600 PAR) and temperature (20-45°C). Three typical Mediterranean plant species (Quercus ilex L., Rosmarinus officinalis L., Pinus halepensis Mill.) with more than three individuals of each have been investigated using a dynamic enclosure cuvette. The terpenoid compound emission rates were found to be directly linked to either light and temperature (e.g. Quercus ilex L.) or mainly to temperature (e.g. Rosmarinus officinalis L., Pinus halepensis Mill.). However, the enantiomeric signature showed no clear trend in response to either the light or temperature; moreover a large variation of enantiomeric enrichment was found during the experiment. This enantiomeric signature was also used to distinguish chemotypes beyond the normal achiral chemical composition method. The results of nineteen Quercus ilex L. individuals, screened under standard conditions (30°C and 1000 PAR) showed four different chemotypes, whereas the traditional classification showed only two. An enclosure branch cuvette set-up was applied in the natural boreal forest environment from four chemotypes of Scots pine (Pinus sylvestris) and one chemotype of Norway spruce (Picea abies) and the direct emissions compared with ambient air measurements above the canopy during the HUMPPA-COPEC 2010 summer campaign. The chirality of a-pinene was dominated by (+)-enantiomers from Scots pine while for Norway spruce the chirality was found to be opposite (i.e. Abstract II (-)-enantiomer enriched) becoming increasingly enriched in the (-)-enantiomer with light. Field measurements over a Spanish stone pine forest were performed to examine the extent of seasonal changes in enantiomeric enrichment (DOMINO 2008). These showed clear differences in chirality of monoterpene emissions. In wintertime the monoterpene (-)-a-pinene was found to be in slight enantiomeric excess over (+)-a-pinene at night but by day the measured ratio was closer to one i.e. racemic. Samples taken the following summer in the same location showed much higher monoterpene mixing ratios and revealed a strong enantiomeric excess of (-)-a-pinene. This indicated a strong seasonal variance in the enantiomeric emission ratio which was not manifested in the day/night temperature cycles in wintertime. A clear diurnal cycle of enantiomeric enrichment in a-pinene was also found over a French oak forest and the boreal forest. However, while in the boreal forest (-)-a-pinene enrichment increased around the time of maximum light and temperature, the French forest showed the opposite tendency with (+)-a-pinene being favored. For the two field campaigns (DOMINO 2008 and HUMPPA-COPEC 2010), the BTEX were also investigated. For the DOMINO campaign, mixing ratios of the xylene isomers (meta- and para-) and ethylbenzene, which are all well resolved on the ß-cyclodextrin column, were exploited to estimate average OH radical exposures to VOCs from the Huelva industrial area. These were compared to empirical estimates of OH based on JNO2 measured at the site. The deficiencies of each estimation method are discussed. For HUMPPA-COPEC campaign, benzene and toluene mixing ratios can clearly define the air mass influenced by the biomass burning pollution plume from Russia.