Time-Resolved Infrared Studies of a Trimethylphosphine Model Derivative of [FeFe]-Hydrogenase

Model compounds that structurally mimic the hydrogen-producing active site of [FeFe]-hydrogenases have been studied to explore potential ground-state electronic structure effects on reaction mechanisms compared to hexacarbonyl derivatives. The time-dependent behavior of Fe₂(μ-S₂C₃H₆)­(CO)₄(PMe)₂ (<b>A</b>) in room temperature <i>n</i>-heptane and acetonitrile solutions was examined using various ultrafast UV and visible excitation pulses with broadband IR-probe spectroscopy of the carbonyl (CO) stretching region. Ground- and excited-state electronic and CO-stretching mode vibrational properties of the possible isomers of <b>A</b> were also examined using density functional theory (DFT) computations. In <i>n</i>-heptane, 355 and 532 nm excitation resulted in short-lived (135 ± 74 ps) bands assigned to excited-state, CO-loss photoproducts. These bands decay away, forming new long-lived absorptions that are likely a mixture of isomers of both three-CO and four-CO ground-state isomers. These new bands grow in with a time scale of 214 ± 119 ps and persist for more than 100 ns. In acetonitrile, similar results are seen with a 532 nm pump, but the 355 nm data lack evidence of the longer-lived bands. In either solvent, the 266 nm pump data seem to also lack longer-lived bands, but the intensities are significantly lower in this data, making firm conclusions more difficult. We suggest that these wavelength-dependent excitation dynamics significantly alter potential mechanisms and efficiencies for light-driven catalysis

The Computational Complexity of Orientation Search in Cryo-Electron Microscopy

In this paper we study the problem of determining threedimensional orientations for noisy projections of randomly oriented identical particles. The problem is of central importance in the tomographic reconstruction of the density map of macromolecular complexes from electron microscope images and it has been studied intensively for more than 30 years