Atomistic characterization of the active-site solvation dynamics of a model photocatalyst

The interactions between the reactive excited state of molecular photocatalysts and surrounding solvent dictate reaction mechanisms and pathways, but are not readily accessible to conventional optical spectroscopic techniques. Here we report an investigation of the structural and solvation dynamics following excitation of a model photocatalytic molecular system [Ir 2 (dimen) 4 ] 2+, where dimen is para-diisocyanomenthane. The time-dependent structural changes in this model photocatalyst, as well as the changes in the solvation shell structure, have been measured with ultrafast diffuse X-ray scattering and simulated with Born-Oppenheimer Molecular Dynamics. Both methods provide direct access to the solute-solvent pair distribution function, enabling the solvation dynamics around the catalytically active iridium sites to be robustly characterized. Our results provide evidence for the coordination of the iridium atoms by the acetonitrile solvent and demonstrate the viability of using diffuse X-ray scattering at free-electron laser sources for studying the dynamics of photocatalysis. © The Author(s) 201617111sciescopu

LADUMA: looking at the distant universe with the MeerKAT array

The cosmic evolution of galaxies’ neutral atomic gas content is a major science driver for the Square Kilometre Array (SKA), as well as for its South African (MeerKAT) and Australian (ASKAP) precursors. Among the H I large survey programs (LSPs) planned for ASKAP and MeerKAT, the deepest and narrowest tier of the “wedding cake” will be defined by the combined L-band+UHF-band Looking At the Distant Universe with the MeerKAT Array (LADUMA) survey, which will probe H I in emission within a single “cosmic vuvuzela” that extends to z = 1.4, when the universe was only a third of its present age. Through a combination of individual and stacked detections (the latter relying on extensive multi-wavelength studies of the survey’s target field), LADUMA will study the redshift evolution of the baryonic Tully–Fisher relation and the cosmic H I density, the variation of the H I mass function with redshift and environment, and the connection between H I content and galaxies’ stellar properties (mass, age, etc.). The survey will also build a sample of OH megamaser detections that can be used to trace the cosmic merger history. This proceedings contribution provides a brief introduction to the survey, its scientific aims, and its technical implementation, deferring a more complete discussion for a future article after the implications of a recent review of MeerKAT LSP project plans are fully worked out

The Photoactive Excited State of the B12-Based Photoreceptor CarH

7 pags., 5 figs.We have used transient absorption spectroscopy in the UV-visible and X-ray regions to characterize the excited state of CarH, a protein photoreceptor that uses a form of B12, adenosylcobalamin (AdoCbl), to sense light. With visible excitation, a nanosecond-lifetime photoactive excited state is formed with unit quantum yield. The time-resolved X-ray absorption near edge structure difference spectrum of this state demonstrates that the excited state of AdoCbl in CarH undergoes only modest structural expansion around the central cobalt, a behavior similar to that observed for methylcobalamin rather than for AdoCbl free in solution. We propose a new mechanism for CarH photoreactivity involving formation of a triplet excited state. This allows the sensor to operate with high quantum efficiency and without formation of potentially dangerous side products. By stabilizing the excited electronic state, CarH controls reactivity of AdoCbl and enables slow reactions that yield nonreactive products and bypass bond homolysis and reactive radical species formation.This work was supported by grants from the National Science Foundation NSF-CHE 1464584 and NSFCHE 1836435 to R.J.S., NSF-CHE 1565795 to K.J.K., NSFCHE 1608553 and NSF-CHE-1904759 to E.N.G.M., and NSF-CHE 1945174 to M.K.; from the Agencia Estatal de Investigación (AEI)-Spain and the European Regional Development Fund (FEDER) grants PGC2018-094635-BC21 (to M.E.-A.) and PGC2018-094635-B-C22 (to S.P.); and from the Fundacion Seneca (Murcia)-Spain grant 20992/PI/ ́ 18 (to M.E.-A.). Portions of this work were carried out in the Laboratory for Ultrafast Multidimensional Optical Spectroscopy (LUMOS) supported by NSF-CHE 1428479. Use of the Linac Coherent Light Source (LCLS), SLAC National Accelerator Laboratory, is supported by the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences under contract no. DE-AC02-76SF00515