Building Blocks for High-Efficiency Organic Photovoltaics: Interplay of Molecular,Crystal, and Electronic Properties in Post-Fullerene ITIC Ensembles

Accurate single-crystal X-ray diffraction data offer a unique opportunity to compare and contrast the atomistic details of bulk heterojunction photovoltaic small-molecule acceptor structure and packing, as well as provide an essential starting point for computational electronic structure and charge transport analysis. Herein, we report diffraction-derived crystal structures and computational analyses on the n-type semiconductors which enable some of the highest efficiency organic solar cells produced to date, 3,9-bis(2-methylene-(3-(1,1-dicyanomethylene)-indanone))-5,5,11,11-tetrakis(4-hexylphenyl)-dithieno[2,3-d:2′,3′-d′]-s-indaceno[1,2-b:5,6-b′]dithiophene ( ITIC ) and seven derivatives (including three new crystal structures: 3,9-bis(2-methylene-(3-(1,1-dicyanomethylene)-indanone))-5,5,11,11-tetrakis(4-propylphenyl)-dithieno[2,3-d:2′,3′-d′]-s-indaceno[1,2-b:5,6-b′]dithiophene ( ITIC-C3 ), 3,9-bis(2-methylene-(3-(1,1-dicyanomethylene)-indanone))-5,5,11,11-tetrakis(3-hexylphenyl)-dithieno[2,3-d:2′,3′-d′]-s-indaceno[1,2-b:5,6-b′]dithiophene ( m -ITIC-C6 ), and 3,9-bis(2-methylene-((3-(1,1-dicyanomethylene)-6,7-difluoro)-indanone))-5,5,11,11-tetrakis(4-butylphenyl)-dithieno[2,3-d:2′,3′-d′]-s-indaceno[1,2-b:5,6-b′]dithiophene ( ITIC-C4-4F ). IDTT acceptors typically pack in a face-to-face fashion with π–π distances ranging from 3.28–3.95 Å. Additionally, edge-to-face packing is observed with S⋯π interactions as short as 3.21–3.24 Å. Moreover, ITIC end group identities and side chain substituents influence the nature and strength of noncovalent interactions (e. g. H-bonding, π–π) and thus correlate with the observed packing motif, electronic structure, and charge transport properties of the crystals. Density functional theory (DFT) calculations reveal relatively large nearest-neighbor intermolecular π-π electronic couplings (5.85–56.8 meV) and correlate the nature of the band structure with the dispersion interactions in the single crystals and core–end group polarization effects. Overall, this combined experimental and theoretical work reveals key insights into crystal engineering strategies for indacenodithienothiophene (IDTT) acceptors, as well as general design rules for high-efficiency post-fullerene small molecule acceptors.     

CO2 hydrogenation to formic acid on Ni(110)

Hydrogen (H) in the subsurface of transition-metal surfaces exhibits unique reactivity for heterogeneously catalyzed hydrogenation reactions. Here, we explore the potential of subsurface H for hydrogenating carbon dioxide (CO₂) on Ni(110). The energetics of surface and subsurface H reacting with surface CO₂ to form formate, carboxyl, and formic acid on Ni(110) is systematically studied using self-consistent, spin-polarized, periodic density functional theory (DFT-GGA-PW91) calculations. We show that on Ni(110), CO₂ can be hydrogenated to formate by surface H. However, further hydrogenation of formate to formic acid by surface H is hindered by a larger activation energy barrier. The relative energetics of hydrogenation barriers is reversed for the carboxyl-mediated route to formic acid. We suggest that the energetics of subsurface H emerging to the surface is suitable for providing the extra energy needed to overcome the barrier to formate hydrogenation. CO₂ hydrogenation to formic acid could take place on Ni(110) when subsurface H is available to react with CO₂. Additional electronic-structure based dynamic calculations would be needed to elucidate the detailed reaction paths for these transformations.     

An Electrochemical Approach to and the Physical Consequences of Preparing Nanostructures from Gold Nanorods with Smooth Ends

We have developed a method to smooth the end sections of nanowires and nanograps generated via the On-Wire Lithography process and studied these rods with optical spectroscopies and theoretical modeling (Discrete Dipole Approximation). The first step of the smoothing process is a reductive one aimed at controlling the diffusion and migration of metal ions to the growing nanorod surface by adjusting the applied potential and concentration of the metal ions in the growth solution. A second oxidative smoothing step, based in part on the energetic differences between topologically rough and smooth surfaces, is used to further smooth the nanorod. The RMS roughness can be reduced over five fold to approximately 5 nm. The properties of these smoothed rods were investigated by empirical and theoretical methods, where it was found the smoothed rods have sharper plasmon resonances and decreased SERS intensity.     

Initial Measurements of Plasma Potential in the Core of the MST Reversed Field Pinch with a Heavy Ion Beam Probe

Measurement of the plasma potential in the core of MST marks both the first interior potential measurements in an RFP, as well as the first measurements by a Heavy Ion Beam Probe (HIBP) in an RFP. The HIBP has operated with (20-110) keV sodium beams in plasmas with toroidal currents of (200-480) kA over a wide range of densities and magnetic equilibrium conditions. A positive plasma potential is measured in the core, consistent with the expectation of rapid electron transport by magnetic fluctuations and the formation of an outwardly directed ambipolar radial electric field. Comparison between the radial electric field and plasma flow is underway to determine the extent to which equilibrium flow is governed by E×B. Measurements of potential and density fluctuations are also in progress.Unlike HIBP applications in tokamak plasmas, the beam trajectories in MST (RFP) are both three-dimensional and temporally dynamic with magnetic equilibrium changes associated with sawteeth. This complication offers new opportunity for magnetic measurements via the Heavy Ion Beam Probe (HIBP). The ion orbit trajectories are included in a Grad-Shafranov toroidal equilibrium reconstruction, helping to measure the internal magnetic field and current profiles. Such reconstructions are essential to identifying the beam sample volume locations, and they are vital in MST's mission to suppress MHD tearing modes using current profile control techniques. Measurement of the electric field may be accomplished by combining single point measurements from multiple discharges, or by varying the injection angle of the beam during single discharges.The application of an HIBP on MST has posed challenges resulting in additional diagnostic advances. The requirement to keep ports small to avoid introducing magnetic field perturbations has led to the design and successful implementation of cross-over sweep systems. High levels of ultraviolet radiation are driving alternative methods of sweep plate operation. While, substantial levels of plasma flux into the HIBP diagnostic chambers has led to the use of magnetic plasma suppression.     

Isochronous Mass Measurements of Hot Exotic Nuclei

A novel method for mass measurements of short-lived exotic nuclides is presented. Exotic nuclides were produced and separated in flight at relativistic energies with the fragment separator (FRS) and were injected into the experimental storage ring (ESR). Operating the ESR in the isochronous mode we performed mass measurements of neutron deficient fragments of ⁸⁴Kr with half-lives larger than 50 ms. However, this experimental technique is applicable in a half-life range down to a few μs. A mass resolving power of 110000 (FWHM) has been achieved. Results are presented for the masses of ⁶⁸As, ^70,71Se and ⁷³Br. This revised version was published online in July 2006 with corrections to the Cover Date.     

Ueber die quantitative Bestimmung des Zuckers

Ohne Zusammenfassung     

Isomers of astrophysical interest in neutron-deficient nuclei at masses A = 81, 85 and 86

Decay properties of neutron-deficient exotic nuclei close to A=80 have been investigated at the IGISOL facility. The studied nuclei, ⁸¹Y, ⁸¹Sr, ^81mKr, ⁸⁵Nb, ⁸⁵Zr, ⁸⁶Mo and ⁸⁶Nb, were produced by a ³²S beam from the Jyv?skyl? isochronous cyclotron on ⁵⁴Fe and ^natNi targets. The internal conversion coefficient for a 190.5 keV isomeric transition in ^81mKr has been measured and the internal transition rate has been determined. The internal transition rate has been used to estimate a neutrino capture rate on ⁸¹Br, which yields a log ft of 5.13±0.09 for the reaction ⁸¹Br( ν, e ^-)^81mKr. A new isomer with a half-life of 3.3±0.9 s has been observed in ⁸⁵Nb. The existence of an earlier reported isomer with a half-life of 56 s in ⁸⁶Nb has not been confirmed.     

Generation of very slow polarized muons by moderation

At the Paul Scherrer Institute very slow, nearly 100% polarized, positive muons with an energy of \sim\mbox10 eV are produced by moderating a secondary beam of surface muons in a thin film of an appropriate condensed gases. These epithermal muons can be used as a source of a tertiary beam of tunable energy between \sim\mbox10 eV and \sim\mbox20 keV. Such a beam allows the μSR technique to be extended to the study of thin films and surfaces. In order to be able to perform time differential μSR experiments we have developed an ultra‐thin detector that registers the passage of keV muons and permits to trigger the experiment. The results achieved so far demonstrate that first investigations of thin film samples can be performed with the present set‐up. This revised version was published online in August 2006 with corrections to the Cover Date.