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Soft X-ray spectroscopies are ideal probes of the local valence electronic structure of photocatalytically active metal sites. Here, we apply the selectivity of time resolved resonant inelastic X-ray scattering at the iron L-edge to the transient charge distribution of an optically excited charge-transfer state in aqueous ferricyanide. Through comparison to steady-state spectra and quantum chemical calculations, the coupled effects of valence-shell closing and ligand-hole creation are experimentally and theoretically disentangled and described in terms of orbital occupancy, metal-ligand covalency, and ligand field splitting, thereby extending established steady-state concepts to the excited-state domain. pi-Back-donation is found to be mainly determined by the metal site occupation, whereas the ligand hole instead influences sigma-donation. Our results demonstrate how ultrafast resonant inelastic X-ray scattering can help characterize local charge distributions around catalytic metal centers in short-lived charge-transfer excited states, as a step toward future rationalization and tailoring of photocatalytic capabilities of transition-metal complexes.
Understanding the rates and pattern of erosion is a key aspect of deciphering the impacts of climate and tectonics on landscape evolution. Denudation rates derived from terrestrial cosmogenic nuclides (TCNs) are commonly used to quantify erosion and bridge tectonic (Myr) and climatic (up to several kiloyears) time scales. However, how the processes of erosion in active orogens are ultimately reflected in Be-10 TCN samples remains a topic of discussion. We investigate this problem in the Arun Valley of eastern Nepal with 34 new Be-10-derived catchment-mean denudation rates. The Arun Valley is characterized by steep north-south gradients in topography and climate. Locally, denudation rates increase northward, from <0.2mmyr(-1) to similar to 1.5mmyr(-1) in tributary samples, while main stem samples appear to increase downstream from similar to 0.2mmyr(-1) at the border with Tibet to 0.91mmyr(-1) in the foreland. Denudation rates most strongly correlate with normalized channel steepness (R-2=0.67), which has been commonly interpreted to indicate tectonic activity. Significant downstream decrease of Be-10 concentration in the main stem Arun suggests that upstream sediment grains are fining to the point that they are operationally excluded from the processed sample. This results in Be-10 concentrations and denudation rates that do not uniformly represent the upstream catchment area. We observe strong impacts on Be-10 concentrations from local, nonfluvial geomorphic processes, such as glaciation and landsliding coinciding with areas of peak rainfall rates, pointing toward climatic modulation of predominantly tectonically driven denudation rates.