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Die Femtosekundendynamik nach resonanten Photoanregungen mit optischen und Röntgenpulsen ermöglicht eine selektive Verformung von chemischen N‐H‐ und N‐C‐Bindungen in 2‐Thiopyridon in wässriger Lösung. Die Untersuchung der orbitalspezifischen elektronischen Struktur und ihrer Dynamik auf ultrakurzen Zeitskalen mit resonanter inelastischer Röntgenstreuung an der N1s‐Resonanz am Synchrotron und dem Freie‐Elektronen‐Laser LCLS in Kombination mit quantenchemischen Multikonfigurationsberechnungen erbringen den direkten Nachweis dieser kontrollierten photoinduzierten Molekülverformungen und ihrer ultrakurzen Zeitskala.
The femtosecond excited-state dynamics following resonant photoexcitation enable the selective deformation of N-H and N-C chemical bonds in 2-thiopyridone in aqueous solution with optical or X-ray pulses. In combination with multiconfigurational quantum-chemical calculations, the orbital-specific electronic structure and its ultrafast dynamics accessed with resonant inelastic X-ray scattering at the N 1s level using synchrotron radiation and the soft X-ray free-electron laser LCLS provide direct evidence for this controlled photoinduced molecular deformation and its ultrashort time-scale.
We present a setup combining a liquid flatjet sample delivery and a MHz laser system for time-resolved soft X-ray absorption measurements of liquid samples at the high brilliance undulator beamline UE52-SGM at Bessy II yielding unprecedented statistics in this spectral range. We demonstrate that the efficient detection of transient absorption changes in transmission mode enables the identification of photoexcited species in dilute samples. With iron(II)-trisbipyridine in aqueous solution as a benchmark system, we present absorption measurements at various edges in the soft X-ray regime. In combination with the wavelength tunability of the laser system, the set-up opens up opportunities to study the photochemistry of many systems at low concentrations, relevant to materials sciences, chemistry, and biology.
The large variety of atmospheric circulation systems affecting the eastern Asian climate is reflected by the complex Asian vegetation distribution. Particularly in the transition zones of these circulation systems, vegetation is supposed to be very sensitive to climate change. Since proxy records are scarce, hitherto a mechanistic understanding of the past spatio-temporal climate-vegetation relationship is lacking. To assess the Holocene vegetation change and to obtain an ensemble of potential mid-Holocene biome distributions for eastern Asia, we forced the diagnostic biome model BIOME4 with climate anomalies of different transient Holocene climate simulations performed in coupled atmosphere-ocean(-vegetation) models. The simulated biome changes are compared with pollen-based biome records for different key regions.
In all simulations, substantial biome shifts during the last 6000 years are confined to the high northern latitudes and the monsoon-westerly wind transition zone, but the temporal evolution and amplitude of change strongly depend on the climate forcing. Large parts of the southern tundra are replaced by taiga during the mid-Holocene due to a warmer growing season and the boreal treeline in northern Asia is shifted northward by approx. 4 degrees in the ensemble mean, ranging from 1.5 to 6 degrees in the individual simulations, respectively. This simulated treeline shift is in agreement with pollen-based reconstructions from northern Siberia. The desert fraction in the transition zone is reduced by 21% during the mid-Holocene compared to pre-industrial due to enhanced precipitation. The desert-steppe margin is shifted westward by 5 degrees (1-9 degrees in the individual simulations). The forest biomes are expanded north-westward by 2 degrees, ranging from 0 to 4 degrees in the single simulations. These results corroborate pollen-based reconstructions indicating an extended forest area in north-central China during the mid-Holocene. According to the model, the forest-to-non-forest and steppe-to-desert changes in the climate transition zones are spatially not uniform and not linear since the mid-Holocene.