TY  - THES
A1  - Pohlenz, Julia
T1  - Structural insights into sodium-rich silicate - carbonate glasses and melts
T1  - Strukturelle Eigenschaften von natriumreichen silikatisch-karbonatischen Gläsern und Schmelzen mittels in-situ XAFS an Spurenelementen und Molekular Dynamik
BT  - a combined study of  trace element in-situ XAFS and Molecular Dynamics
N2  - Carbonate-rich silicate and carbonate melts play a crucial role in deep Earth magmatic processes and their melt structure is a key parameter, as it controls physical and chemical properties. Carbonate-rich melts can be strongly  enriched in geochemically important trace elements. The structural incorporation mechanisms of these elements are difficult to study because such melts generally cannot be quenched to glasses, which are usually employed for structural investigations. This thesis investigates the influence of CO2 on the local environments of trace elements contained in silicate glasses with variable CO2 concentrations as well as in silicate and carbonate melts. The compositions studied include sodium-rich peralkaline silicate melts and glasses and carbonate melts similar to those occurring naturally at Oldoinyo Lengai volcano, Tanzania. 
The local environments of the three elements yttrium (Y), lanthanum (La) and strontium (Sr) were investigated in synthesized glasses and melts using X-ray absorption fine structure (XAFS) spectroscopy. Especially extended X-ray  absorption fine structure spectroscopy (EXAFS) provides element specific  information on local structure, such as bond lengths, coordination numbers and the degree of disorder. To cope with the enhanced structural disorder present in glasses and melts, EXAFS analysis was based on fitting approaches using an asymmetric distribution function as well as a correlation model according to bond valence theory. Firstly, silicate glasses quenched from high pressure/temperature melts with up to 7.6 wt % CO2 were investigated. In strongly and extremely peralkaline glasses the local structure of Y is unaffected by the CO2 content (with oxygen bond lengths of ~ 2.29 Å). Contrary, the bond lengths for Sr-O and La-O increase with increasing CO2 content in the strongly peralkaline glasses from ~ 2.53 to ~ 2.57 Å and from ~ 2.52 to ~ 2.54 Å, respectively, while they remain constant in extremely peralkaline glasses (at ~ 2.55 Å and 2.54 Å, respectively). Furthermore, silicate and unquenchable carbonate melts were investigated in-situ at high pressure/temperature conditions (2.2 to 2.6 GPa, 1200 to 1500 °C) using a Paris-Edinburgh press. A novel design of the pressure medium assembly for this press was developed, which features  increased mechanical stability as well as enhanced transmittance at relevant energies to allow for low content element EXAFS in transmission. Compared to glasses the bond lengths of Y-O, La-O and Sr-O are elongated by up to + 3 % in the melt and exhibit higher asymmetric pair distributions. For all investigated silicate melt compositions Y-O bond lengths were found constant at ~ 2.37 Å, while in the carbonate melt the Y-O length increases slightly to 2.41 Å. The La-O bond lengths in turn, increase systematically over the whole silicate – carbonate melt joint from 2.55 to 2.60 Å. Sr-O bond lengths in melts increase from ~ 2.60 to 2.64 Å from pure silicate to silicate-bearing carbonate composition with constant elevated bond length within the carbonate region. 
For comparison and deeper insight, glass and melt structures of Y and Sr bearing sodium-rich silicate to carbonate compositions were simulated in an explorative ab initio molecular dynamics (MD) study. The simulations confirm  observed patterns of CO2-dependent local changes around Y and Sr and additionally provide further insights into detailed incorporation mechanisms of the trace elements and CO2. Principle findings include that in sodium-rich silicate compositions carbon either is mainly incorporated as a free carbonate-group or shares one oxygen with a network former (Si or [4]Al) to form a non-bridging carbonate. Of minor importance are bridging carbonates between two network formers. Here, a clear preference for two [4]Al as adjacent network formers occurs, compared to what a statistical distribution would suggest. In C-bearing silicate melts minor amounts of molecular CO2 are present, which is almost totally dissolved as carbonate in the quenched glasses.
The combination of experiment and simulation provides extraordinary insights into glass and melt structures. The new data is interpreted on the basis of bond valence theory and is used to deduce potential mechanisms for structural incorporation of investigated elements, which allow for prediction on their partitioning behavior in natural melts. Furthermore, it provides unique insights into the dissolution mechanisms of CO2 in silicate melts and into the carbonate melt structure. For the latter, a structural model is suggested, which is based on planar CO3-groups linking 7- to 9-fold cation polyhedra, in accordance to structural units as found in the Na-Ca carbonate nyerereite. Ultimately, the outcome of this study contributes to rationalize the unique physical properties and geological phenomena related to carbonated silicate-carbonate melts.
N2  - Karbonatische und karbonatreiche silikatische Schmelzen spielen eine entscheidende Rolle in den magmatischen Prozessen der Erde. Die interne Schmelzstruktur bestimmt dabei maßgeblich ihre physikalischen und chemischen Eigenschaften. Karbonatreiche Schmelzen können sehr stark mit geochemisch wichtigen Spurenelementen angereichert sein. Die strukturellen Einbaumechanismen sind jedoch kaum verstanden, da diese Schmelzen nicht zu homogenen Gläsern abgeschreckt werden können, welche üblicherweise für strukturelle Untersuchungen genutzt werden. Die vorliegende Arbeit widmet sich dem Einfluss von CO2 auf die lokale Umgebung von ausgewählten Spurenelementen in karbonathaltigen silikatischen Gläsern sowie silikatisch bis karbonatischen Schmelzen. Untersucht werden natriumreiche, stark bis extrem peralkaline silikatische und karbonatische Zusammensetzungen, wie sie vom Vulkan Oldoinyo Lengai, Tansania, bekannt sind.
Zum einen werden die lokale Umgebungen von Yttrium (Y), Lanthan (La) und Strontium (Sr) in synthetisierten Gläsern und Schmelzen mit Röntgen-Absorption-Feinstruktur-Spektroskopie (engl. X-ray absorption fine structure (XAFS) spectroscopy) untersucht. Insbesondere extended X-ray absorption fine structure (EXAFS) spectroscopy liefert elementspezifisch strukturelle Informationen über Bindungslängen, Koordinationszahlen und Ordnungsgrad. Dem hohen Grad struktureller Unordnung in Gläsern und Schmelzen wird in den vorliegenden EXAFS-Analysen mit der Verwendung einer asymmetrischen Verteilungsfunktion und eines Korrelationsmodells, basierend auf der Bindungsvalenztheorie, Rechnung getragen. Für silikatische Gläser mit steigendem CO2-Gehalt zwischen 0 und bis zu 7,6 Gew.-% ist festzustellen: (1) Konstante Bindungslängen für Sr-O (~ 2,55 Å) und La-O (~ 2,54 Å) in extrem peralkaliner Zusammensetzung, sowie für Y-O (~ 2,29 Å) in stark und extrem peralkaliner Zusammensetzung. (2) Zunehmende Bindungslängen für Sr-O (~ von 2,53 auf 2,57 Å) und La-O in stark peralkaliner Zusammensetzung (~ von 2,52 auf 2,54 Å). Weiterhin werden silikatische sowie nicht-abschreckbare karbonatische Schmelzen in-situ unter hohem Druck und hoher Temperatur (2,2 bis 2,6 GPa, 1200 bis 1500 °C, untersucht in einer Paris-Edinburgh-Presse) analysiert. Ein neu entwickelter Aufbau des Druckübertragungsmediums garantiert eine hohe mechanische Festigkeit und ermöglicht aufgrund hervorragender Transmissivität im relevanten Energiebereich Transmissions-EXAFS an niedrigkonzentrierten Elementen. Im Vergleich zu den Gläsern zeigen die Schmelzen generell ~ 3 % höhere Y-O-, La-O-, und Sr-O-Bindungslängen und eine erhöhte Asymmetrie in der Paarverteilung. In silikatischen Schmelzen sind Y-O-Bindungslängen konstant (~ 2,37 Å), wohingegen sie in karbonatischen Schmelzen zunehmen (bis zu 2,41 Å). La-O-Abstände vergrößern sich systematisch von silikatischen zu karbonatischen Schmelzen (von 2,55 auf 2,60 Å). Sr-O-Abstände steigen von 2,60 auf 2,64 Å in silikatischen Zusammensetzungen mit steigendem CO2-Gehalt und sind für alle karbonatischen Zusammensetzungen konstant.
Zum Vergleich und besserem Verständnis wurden Y- und Sr-haltige, silikatische und karbonatische Glas- und Schmelzstrukturen in einer explorativen ab-initio Molekular Dynamik (MD) Studie simuliert. Die MD-Studie bestätigt die CO2-abhängigen lokalen Veränderungen um Y und Sr und liefert zusätzliche Einblicke in silikatische und karbonatische Glas- und Schmelzstrukturen. In natriumreicher silikatischer Zusammensetzung wird CO2 hauptsächlich als freie Karbonatgruppe eingebaut oder teilt sich als nicht-brückenbildendes Karbonat genau ein Sauerstoffatom mit einem Netzwerkbildner (Si oder [4]Al). Seltener tritt es als brückenbildendes Karbonat zwischen zwei Netzwerkbildnern auf; dabei allerdings mit einer gegenüber der statistischen Verteilung deutlich erhöhten Präferenz für zwei [4]Al als anliegende Netzwerkbildner. C-haltige Schmelzen weisen geringe Mengen an molekularem CO2 auf, welches in den abgeschreckten Gläsern fast vollständig als Karbonat gelöst ist.
Die Kombination aus Experiment und Simulation gewährt außerordentliche Einblicke in nur schwierig zu untersuchende Glas- und Schmelzstrukturen. Die gewonnenen Daten werden auf Grundlage der Bindungsvalenztheorie gedeutet und hinsichtlich potentieller Mechanismen des strukturellen Spurenelementeinbaus sowie dem daraus ableitbaren Fraktionierungsverhalten in natürlichen Schmelzen diskutiert. Neue Erkenntnisse über den strukturellen CO2-Einbau werden genutzt, um ein Strukturmodell für karbonatische Schmelzen abzuleiten. Dieses basiert auf der Verknüpfung von 7- bis 9-fach koordinierten Kationenpolyedern durch die planaren Karbonat-Gruppen, ähnlich wie es im Na-Ca-Karbonat Nyerereite zu beobachten ist. Letztendlich leisten die Erkenntnisse der Arbeit somit ihren Beitrag, das Verständnis um die einzigartigen physikalischen Eigenschaften und geologischen Phänomene dieser Schmelzen zu vertiefen.
KW  - glass structure
KW  - melt structure
KW  - X-ray absorption spectroscopy
KW  - Glasstruktur
KW  - Schmelzstruktur
KW  - Röntgenabsorptionsspektroskopie
Y1  - 2019
U6  - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:kobv:517-opus4-423826
ER  - 
TY  - THES
A1  - Born, Artur
T1  - Electronic structure, quasi-particle interaction and relaxation in 3d-elements from X-ray spectroscopy
N2  - Any physical system can be described on the level of interacting particles, thus it is of fundamental importance to improve the scientific understanding of interacting many-body systems. This thesis experimentally addresses specific quasi-particle interactions, namely interactions be- tween electrons and between electrons and phonons. It describes the consequential effects of those processes on the electronic structure and the core-hole relaxation pathways in 3d metals. Despite the great amount of experimental and theoretical studies of these interactions and their impact on the behavior of solid-state matter, there are still open questions concerning the cor- responding physical, chemical and mechanical properties of solid-state matter. Especially, the study of 3d metals and their compounds is a great experimental challenge, since those exhibit a variety of spectral features originating from many-body effects such as multiplet splitting, shake up/off satellites, vibrationally excited states or more complex effects like superconductivity and ultrafast demagnetization. In X-ray spectroscopy, these effects often produce overlapping fea- tures, complicating the analysis and limiting the understanding. In this thesis, to overcome the limitations set by conventional X-ray spectroscopy, two different experimental approaches were successfully refined, namely Auger electron photoelectron coincidence spectroscopy (APECS) and temperature-dependent X-ray emission spectroscopy (tXES), which enabled the separation of different core-hole relaxation pathways and the isolation of the impact of specific many-body interactions in the experimental spectra. APECS was utilized at the new Coincidence electron spectroscopy for chemical analysis (Co- ESCA) station at BESSY II to study the core-hole decay and electron-correlation effects in single- crystal Ni, Cu and Co. The observation of photoelectrons in coincidence with Auger electrons allows for the separation of the initial and final state effects in the Auger electron spectra. The results show that a Cu LV V Auger spectrum can be represented by broadened atomic multiplets confirming the localized nature of the intermediate core-hole states. In contrast, the Co LV V Auger spectrum is band-like and can be represented by the self-convolution of the valence band. Ni behaves mixed, localized and itinerant. Thus, the Ni Auger spectrum can only be represented by a mixture of atomic multiplet peaks and the self-convoluted valence band. In the case of Ni, the LV V Auger electrons in coincidence with the 6 eV satellite photoelectrons were also stud- ied. Utilizing the core-hole clock method, the lifetime of the localized double-hole intermediate 2 p53d9 states of 1.8 fs could be determined. However, a fraction of these states delocalizes before the Auger decay contributing to the main peak. A similar delocalization was observed for the double-hole states produced by the L2L3M4,5 Coster-Kronig process. Additionally, the influence of surface oxidation on the Ni(111) 3p levels was studied with APECS. The Ni 3p PES spectrum is broad and featureless, due to overlapping many-body effects and gives little chance for exact analysis using conventional photoelectron spectroscopy. Utilizing APECS or precisely the final state selectivity of the method, the spectral width of the 3p levels could be narrowed and their positions and the spin-orbit splitting were determined. Moreover, due to the surface sensitivity of the method, the chemically shifted 3p photoelectron peaks originating from the oxidized surface and the bulk Ni were disentangled. For the study of the atomic electron-phonon spin-flip scattering in 3d metals as a spin-relaxation channel, the tXES method at the SolidFlexRIXS station was developed. The atomic spin-flip scat- tering was studied in single-crystal Ni, Cu, Co and in FeNi alloys, which show considerable dif- ferences in their behavior. The scattering rate in Ni increases with temperature, whereas the rate in Cu and Co remains constant within the measured temperature range up to 1000 K. In FeNi alloys, our results reveal that the spin-flip scattering is restricted by sublattice exchange energies J. The electron-phonon scattering driven spin-flips only appear in the case where the thermal energy ex- ceeds the exchange energy kT > J. This thresholding is an important microscopic process for the description of the sublattice dynamics in alloys, but as shown also relevant for elemental magnetic systems. Overall, the results strongly indicate that the spin-flip probability is correlated with the exchange energy, which might become an important parameter in the ultrafast demagnetization debate. Taken together, the applied experimental approaches allowed to study complex many-body effects in 3d metals. The results show that utilizing APECS enabled the distinction and clear assignment of otherwise overlapping features in AES or PES spectra of Ni, Cu, Co and NiO. This is of fundamental importance for the basic understanding of photoionization and core-hole decay processes but also for the chemical analysis in applied science. The measurement of the atomic electron-phonon spin-flip scattering rate utilizing tXES shows that the electron-phonon spin-flip scattering is a relevant atomic process for the macroscopic demagnetization process. Additionally, a temperature-dependent thresholding mechanism was discovered, which introduces an important dynamic factor into the electron-phonon spin-flip model.
KW  - X-ray spectroscopy
KW  - photoelectron spectroscopy
KW  - Auger electron spectroscop
KW  - X-ray absorption spectroscopy
KW  - X-ray emission spectroscopy
KW  - 3d metals
KW  - electronic structure
KW  - quasi-particle interaction
Y1  - 2021
ER  -