Numerous studies have shown that the performance of hematite photoanodes for light-driven water splitting is improved substantially by doping with various metals, including tin. Although the enhanced performance has commonly been attributed to bulk effects such as increased conductivity, recent studies have noted an impact of doping on the efficiency of the interfacial transfer of holes involved in the oxygen evolution reaction. However, the methods used were not able to elucidate the origin of this improved efficiency, which could originate from passivation of surface electron-hole recombination or catalysis of the oxygen evolution reaction. The present study used intensity-modulated photocurrent spectroscopy (IMPS), which is a powerful small amplitude perturbation technique that can de-convolute the rate constants for charge transfer and recombination at illuminated semiconductor electrodes. The method was applied to examine the kinetics of water oxidation on thin solution-processed hematite model photoanodes, which can be Sn-doped without morphological change. We observed a significant increase in photocurrent upon Sn-doping, which is attributed to a higher transfer efficiency. The kinetic data obtained using IMPS show that Sn-doping brings about a more than tenfold increase in the rate constant for water oxidation by photogenerated holes. This result provides the first demonstration that Sn-doping speeds up water oxidation on hematite by increasing the rate constant for hole transfer.

The recently discovered lithium-rich cathode material Li7Mn(BO3)3 has a high theoretical capacity and an unusual tetrahedral Mn(2+) coordination. Atomistic simulation and density functional theory (DFT) techniques are employed to provide insights into the defect and redox chemistry, the structural changes upon lithium extraction and the mechanisms of lithium ion diffusion. The most favourable intrinsic defects are Li/Mn anti-site pairs, where Li and Mn ions occupy interchanged positions, and Li Frenkel defects. DFT calculations reproduce the experimental cell voltage and confirm the presence of the unusually high Mn(V) redox state, which corresponds to a theoretical capacity of nearly 288 mA h g(-1). The ability to reach the high manganese oxidation state is related to both the initial tetrahedral coordination of Mn and the observed distortion/tilting of the BO3 units to accommodate the contraction of the Mn-O bonds upon oxidation. Molecular dynamics (MD) simulations indicate fast three-dimensional lithium diffusion in line with the good rate performance observed.

We analyze the dynamics of a spin 1/2 subsystem coupled to a spin chain. We simulate numerically the full quantum many-body system for various sets of parameters and initial states of the chain, and characterize the divisibility of the subsystem dynamics, i.e. whether it is Markovian and can be described by a (time dependent) master equation. We identify regimes in which the subsystem admits such Markovian description, despite the many-body setting, and provide insight about why the same is not possible in other regimes. Interestingly, coupling the subsystem at the edge, instead of the center, of the chain gives rise to qualitatively distinct behavior.