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Anti-Stokes resonant x-ray Raman scattering for atom specific and excited state selective dynamics
(2016)
Ultrafast electronic and structural dynamics of matter govern rate and selectivity of chemical reactions, as well as phase transitions and efficient switching in functional materials. Since x-rays determine electronic and structural properties with elemental, chemical, orbital and magnetic selectivity, short pulse x-ray sources have become central enablers of ultrafast science. Despite of these strengths, ultrafast x-rays have been poor at picking up excited state moieties from the unexcited ones. With time-resolved anti-Stokes resonant x-ray Raman scattering (AS-RXRS) performed at the LCLS, and ab initio theory we establish background free excited state selectivity in addition to the elemental, chemical, orbital and magnetic selectivity of x-rays. This unparalleled selectivity extracts low concentration excited state species along the pathway of photo induced ligand exchange of Fe(CO)(5) in ethanol. Conceptually a full theoretical treatment of all accessible insights to excited state dynamics with AS-RXRS with transform-limited x-ray pulses is given-which will be covered experimentally by upcoming transform-limited x-ray sources.
The valence-excited states of ferric and ferrous hexacyanide ions in aqueous solution were mapped by resonant inelastic X-ray scattering (RIXS) at the Fe L-2,L-3 and N K edges. Probing of both the central Fe and the ligand N atoms enabled identification of the metal-and ligand-centered excited states, as well as ligand-to-metal and metal-to-ligand charge-transfer excited states. Ab initio calculations utilizing the RASPT2 method were used to simulate the Fe L-2,L-3-edge RIXS spectra and enabled quantification of the covalencies of both occupied and empty orbitals of pi and sigma symmetry. We found that pi back-donation in the ferric complex is smaller than that in the ferrous complex. This is evidenced by the relative amounts of Fe 3d character in the nominally 2 pi CN- molecular orbital of 7% and 9% in ferric and ferrous hexacyanide, respectively. Utilizing the direct sensitivity of Fe L-3-edge RIXS to the Fe 3d character in the occupied molecular orbitals, we also found that the donation interactions are dominated by sigma bonding. The latter was found to be stronger in the ferric complex, with an Fe 3d contribution to the nominally 5 sigma CN- molecular orbitals of 29% compared to 20% in the ferrous complex. These results are consistent with the notion that a higher charge at the central metal atom increases donation and decreases back-donation.
Recombination of free charge is a key process limiting the performance of solar cells. For low mobility materials, such as organic semiconductors, the kinetics of non-geminate recombination (NGR) is strongly linked to the motion of charges. As these materials possess significant disorder, thermalization of photogenerated carriers in the inhomogeneously broadened density of state distribution is an unavoidable process. Despite its general importance, knowledge about the kinetics of NGR in complete organic solar cells is rather limited. We employ time delayed collection field (TDCF) experiments to study the recombination of photogenerated charge in the high-performance polymer:fullerene blend PCDTBT:PCBM. NGR in the bulk of this amorphous blend is shown to be highly dispersive, with a continuous reduction of the recombination coefficient throughout the entire time scale, until all charge carriers have either been extracted or recombined. Rapid, contact-mediated recombination is identified as an additional loss channel, which, if not properly taken into account, would erroneously suggest a pronounced field dependence of charge generation. These findings are in stark contrast to the results of TDCF experiments on photovoltaic devices made from ordered blends, such as P3HT:PCBM, where non-dispersive recombination was proven to dominate the charge carrier dynamics under application relevant conditions.
Recombination of free charge is a key process limiting the performance of solar cells. For low mobility materials, such as organic semiconductors, the kinetics of non-geminate recombination (NGR) is strongly linked to the motion of charges. As these materials possess significant disorder, thermalization of photogenerated carriers in the inhomogeneously broadened density of state distribution is an unavoidable process. Despite its general importance, knowledge about the kinetics of NGR in complete organic solar cells is rather limited. We employ time delayed collection field (TDCF) experiments to study the recombination of photogenerated charge in the high-performance polymer:fullerene blend PCDTBT:PCBM. NGR in the bulk of this amorphous blend is shown to be highly dispersive, with a continuous reduction of the recombination coefficient throughout the entire time scale, until all charge carriers have either been extracted or recombined. Rapid, contact-mediated recombination is identified as an additional loss channel, which, if not properly taken into account, would erroneously suggest a pronounced field dependence of charge generation. These findings are in stark contrast to the results of TDCF experiments on photovoltaic devices made from ordered blends, such as P3HT:PCBM, where non-dispersive recombination was proven to dominate the charge carrier dynamics under application relevant conditions.
Recombination of free charge is a key process limiting the performance of solar cells. For low mobility materials, such as organic semiconductors, the kinetics of non-geminate recombination (NGR) is strongly linked to the motion of charges. As these materials possess significant disorder, thermalization of photogenerated carriers in the inhomogeneously broadened density of state distribution is an unavoidable process. Despite its general importance, knowledge about the kinetics of NGR in complete organic solar cells is rather limited. We employ time delayed collection field (TDCF) experiments to study the recombination of photogenerated charge in the high-performance polymer: fullerene blend PCDTBT:PCBM. NGR in the bulk of this amorphous blend is shown to be highly dispersive, with a continuous reduction of the recombination coefficient throughout the entire time scale, until all charge carriers have either been extracted or recombined. Rapid, contact-mediated recombination is identified as an additional loss channel, which, if not properly taken into account, would erroneously suggest a pronounced field dependence of charge generation. These findings are in stark contrast to the results of TDCF experiments on photovoltaic devices made from ordered blends, such as P3HT:PCBM, where non-dispersive recombination was proven to dominate the charge carrier dynamics under application relevant conditions.
We consider a system of three interacting van der Pol oscillators with reactive coupling. Phase equations are derived, using proper order of expansion over the coupling parameter. The dynamics of the system is studied by means of the bifurcation analysis and with the method of Lyapunov exponent charts. Essential and physically meaningful features of the reactive coupling are discussed.
Equations are derived for a parametric chaos generator containing three oscillatory circuits and a variable-capacitance diode (varactor) and are reduced to equations for slow amplitudes of parametrically interacting modes. With allowance for quadratic nonlinearity, the problem is reduced to a system of three first-order differential equations for Pikovsky-Rabinovich-Trakhtengerts real amplitudes with a Lorenz-type attractor. In a more accurate description of nonlinearity of the varactor, the equations for slow amplitudes are complex-valued, which leads to the loss of robustness of chaotic dynamics, which is typical of the Lorenz attractor. The results of numerical calculations (portraits of attractors and Lyapunov exponents) in models with different approximation levels are compared.
The density of firn is an important property for monitoring and modeling the ice sheets as well as to model the pore close-off and thus to interpret ice core-based greenhouse gas records. One feature, which is still in debate, is the potential existence of an annual cycle of firn density in low-accumulation regions. Several studies describe or assume seasonally successive density layers, horizontally evenly distributed, as seen in radar data. On the other hand, high-resolution density measurements on firn cores in Antarctica and Greenland show no clear seasonal cycle in the top few meters. A major caveat of most existing snow-pit and firn-core-based studies is that they represent one vertical profile from a laterally heterogeneous density field. To overcome this, we created an extensive data set of horizontal and vertical density data at Kohnen Station, Dronning Maud Land, on the East Antarctic Plateau. We drilled and analyzed three 90m long firn cores as well as 143 one-meter-long vertical profiles from two elongated snow trenches to obtain a two-dimensional view of the density variations. The analysis of the 45m wide and 1m deep density fields reveals a seasonal cycle in density. However, the seasonality is overprinted by strong stratigraphic noise, making it invisible when analyzing single firn cores. Our density data set extends the view from the local ice core perspective to a hundred meter scale and thus supports linking spatially integrating methods such as radar and seismic studies to ice and firn cores.
Hydrological and climatological controls on radiocarbon concentrations in a tropical stalagmite
(2016)
Precisely-dated stalagmites are increasingly important archives for the reconstruction of terrestrial paleoclimate at very high temporal resolution. In-depth understanding of local conditions at the cave site and of the processes driving stalagmite deposition is of paramount importance for interpreting proxy signals incorporated in stalagmite carbonate. Here we present a sub-decadally resolved dead carbon fraction (DCF) record for a stalagmite from Yok Balum Cave (southern Belize). The record is coupled to parallel stable carbon isotope (delta C-13) and U/Ca measurements, as well as radiocarbon (C-14) measurements from soils overlying the cave system. Using a karst carbon cycle model we disentangle the importance of soil and karst processes on stalagmite DCF incorporation, revealing a dominant host rock dissolution control on total DCF. Covariation between DCF, delta C-13, and U/Ca indicates that karst processes are a common driver of all three parameters, suggesting possible use of delta C-13 and trace element ratios to independently quantify DCF variability. A statistically significant multi-decadal lag of variable length exists between DCF and reconstructed solar activity, suggesting that solar activity influenced regional precipitation in Mesoamerica over the past 1500 years, but that the relationship was non-static. Although the precise nature of the observed lag is unclear, solar-induced changes in North Atlantic oceanic and atmospheric dynamics may play a role. (C) 2016 Elsevier Ltd. All rights reserved.