Model compounds have been found to structurally mimic the catalytic hydrogen-producing active site of Fe-Fe hydrogenases and are being explored as functional models. The time-dependent behavior of Fe(2)(μ-S(2)C(3)H(6))(CO)(6) and Fe(2)(μ-S(2)C(2)H(4))(CO)(6) is reviewed and new ultrafast UV- and visible-excitation/IR-probe measurements of the carbonyl stretching region are presented. Ground-state and excited-state electronic and vibrational properties of Fe(2)(μ-S(2)C(3)H(6))(CO)(6) were studied with density functional theory (DFT) calculations. For Fe(2)(μ-S(2)C(3)H(6))(CO)(6) excited with 266 nm, long-lived signals (τ = 3.7 ± 0.26 μs) are assigned to loss of a CO ligand. For 355 and 532 nm excitation, short-lived (τ = 150 ± 17 ps) bands are observed in addition to CO-loss product. Short-lived transient absorption intensities are smaller for 355 nm and much larger for 532 nm excitation and are assigned to a short-lived photoproduct resulting from excited electronic state structural reorganization of the Fe-Fe bond. Because these molecules are tethered by bridging disulfur ligands, this extended di-iron bond relaxes during the excited state decay. Interestingly, and perhaps fortuitously, the time-dependent DFT-optimized exited-state geometry of Fe(2)(μ-S(2)C(3)H(6))(CO)(6) with a semibridging CO is reminiscent of the geometry of the Fe(2)S(2) subcluster of the active site observed in Fe-Fe hydrogenase X-ray crystal structures. We suggest these wavelength-dependent excitation dynamics could significantly alter potential mechanisms for light-driven catalysis.

Vapor deposited thin films of copper phthalocyanine (CuPc) were investigated using transient absorption spectroscopy. Exciton-exciton annihilation dominated the kinetics at high exciton densities. When annihilation was minimized, the observed lifetime was measured to be 8.6 AE 0.6 ns, which is over an order of magnitude longer than previous reports. In comparison with metal free phthalocyanine (H 2 Pc), the data show evidence that the presence of copper induces an ultrafast relaxation process taking place on the ca. 500 fs timescale.By comparison to recent time-resolved photoemission studies, this is assigned as ultrafast intersystem crossing. As the intersystem crossing occurs ca. 10 4 times faster than lifetime decay, it is likely that triplets are the dominant excitons in vapor deposited CuPc films. The exciton lifetime of CuPc thin films is ca. 35 times longer than H 2 Pc thin films, while the diffusion lengths reported in the literature are typically quite similar for the two materials. These findings suggest that despite appearing to be similar materials at first glance, CuPc and H 2 Pc may transport energy in dramatically different ways. This has important implications on the design and mechanistic understanding of devices where phthalocyanines are used as an excitonic material.

A phthalocyanine/Ag(111) interface state is observed for the first time using time- and angle-resolved two-photon photoemission. For monolayer films of metal-free (H2Pc) and iron phthalocyanine (FePc) on Ag(111), the state exists 0.23 ± 0.03 and 0.31 ± 0.03 eV above the Fermi level, respectively. Angle-resolved spectra show the state to be highly dispersive with an effective mass of 0.50 ± 0.15 me for H2Pc and 0.67 ± 0.14 me for FePc. Density functional theory calculations on the H2Pc/Ag(111) surface allow us to characterize this state as being a hybrid state resulting from the interaction between the unoccupied molecular states of the phthalocyanine ligand and the Shockley surface state present on the bare Ag(111) surface. This work, when taken together with the extensive literature on the 3,4,9,10-perylene tetracarboxylic dianhydride/Ag interface state, provides compelling evidence that the hybridization of metal surface states with molecular electronic states is a general phenomenon.

Across all disciplines that work with image data -from astrophysics to medical research and historic preservation -there is a growing need for efficient ways to browse and inspect large sets of high-resolution images. We present the development of a visualization software for solar physics data based on the JPEG 2000 image compression standard. Our implementation consists of the JHelioviewer client application that enables users to browse petabyte-scale image archives and the JHelioviewer server, which integrates a JPIP server, metadata catalog and an event server. JPEG 2000 offers many useful new features and has the potential to revolutionize the way high-resolution image data are disseminated and analyzed. This is especially relevant for solar physics, a research field in which upcoming space missions will provide more than a terabyte of image data per day. Providing efficient access to such large data volumes at both high spatial and high time resolution is of paramount importance to support scientific discovery.

Electron solvation is examined at the interface of a room temperature ionic liquid (RTIL) and an Ag(111) electrode. Femtosecond two-photon photoemission spectroscopy is used to inject an electron into an ultrathin film of RTIL 1-butyl-1-methylpyrrolidinium bis(trifluoromethylsulfonyl)imide ([Bmpyr](+)[NTf2](-)). While much of current literature highlights slower nanosecond solvation mechanisms in bulk ionic liquids, we observe only a femtosecond response, supporting morphology dependent and interface specific electron solvation mechanisms. The injected excess electron is found to reside in an electron affinity level residing near the metal surface. Population of this state decays back to the metal with a time constant of 400 ± 150 fs. Electron solvation is measured as a dynamic decrease in the energy with a time constant of 350 ± 150 fs. We observe two distinct temperature regimes, with a critical temperature near 250 K. The low temperature regime is characterized by a higher work function of 4.41 eV, while the high temperature regime is characterized by a lower work function of 4.19 eV. The total reorganizational energy of solvation changes above and below the critical temperature. In the high temperature regime, the electron affinity level solvates by 540 meV at 350 K, and below the critical temperature, solvation decreases to 200 meV at 130 K. This study will provide valuable insight to interface specific solvation of room temperature ionic liquids.