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This presentation has been moved. To view this presentation, please visit http://pubs.acs.org/iapps/liveslides/pages/index.htm?mscNo=jz300754p Bulk Heterojunction versus Diffused Bilayer: The Role of Device Geometry in Solution p-Doped Polymer-Based Solar Cells Anna Loiudice, Aurora Rizzo, Mariano Biasiucci, and Giuseppe Gigli J. Phys. Chem. Lett., 2012, 3 (14), pp 1908–1915 We exploit the effect of molecular p-type doping of P3HT in diffused bilayer (DB) polymer solar cells. In this alternative device geometry, the p-doping is accomplished in solution by blending the F4-TCNQ with P3HT. The p-doping both increases the film conductivity and reduces the potential barrier at the interface with the electrode. This results in an excellent power conversion efficiency of 4.02%, which is an improvement of 48% over the p-doped standard bulk heterojunction (BHJ) device. Combined VOC–light intensity dependence measurements and Kelvin probe force microscopy reveal that the DB device configuration is particularly advantageous, if compared to the conventional BHJ, because it enables optimization of the donor and acceptor layers independently to minimize the effect of trapping and to fully exploit the improved transport properties.

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This presentation has been moved. To view this presentation, please visit http://pubs.acs.org/iapps/liveslides/pages/index.htm?mscNo=jz3004014 Ag@SiO2 Core–Shell Nanostructures: Distance-Dependent Plasmon Coupling and SERS Investigation J. Phys. Chem. Lett., 2012, 3 (11), pp 1459–1464 Enhancement of Raman signals of pyrene due to the enhanced electric fields on the surface of silver nanoparticles has been investigated by controlling the thickness of the silica shell. Dimeric nanostructures having well-defined gaps between two silver nanoparticles were prepared, and the gap size (d) was varied from 1.5 to 40 nm. The molecules trapped at the dimeric junctions showed higher Raman signal enhancements when the gap was less than 15 nm due to the presence of amplified electric field, in agreement with our theoretical studies. The experimental Raman enhancement factors at the hot spots follow a 1/dn dependence, with n = 1.5, in agreement with the recent theoretical studies by Schatz and co-workers. Experimental results presented here on the distance dependence of surface enhanced Raman spectroscopy (SERS) enhancement at the hot spots can provide insight on the design of newer plasmonic nanostructures with optimal nanogaps.

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This presentation has been moved. To view this presentation, please visit http://pubs.acs.org/iapps/liveslides/pages/index.htm?mscNo=jz300577e The Effect of the π-Electron Delocalization Curvature on the Two-Photon Circular Dichroism of Molecules with Axial Chirality Herein we report on the theoretical-experimental study of the effect of curvature of the π-electron delocalization on the two-photon circular dichroism (TPCD) of a family of optically active biaryl derivatives (S-BINOL, S-VANOL, and S-VAPOL). The comparative analysis of the influence of the different transition moments to their corresponding TPCD rotatory strength reveals an enhanced contribution of the magnetic transition dipole moment on VAPOL. This effect is hereby attributed to the additional twist in the π–electron delocalization on this compound. TPCD measurements were done using the double L-scan technique in the picosecond regime. Theoretical calculations were completed using modern analytical response theory, within a time-dependent density functional theory (TD-DFT) approach, at both, B3LYP and CAM-B3LYP levels, with the aug-cc-pVDZ basis set for S-BINOL and S-VANOL, and 6-31G* for S-VAPOL. Solvent effects were included by means of the polarizable continuum model (PCM) in CH2Cl2.

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This presentation has been moved. To view this presentation, please visit http://pubs.acs.org/iapps/liveslides/pages/index.htm?mscNo=jz300574u Atomically Resolved Site-Isolated Catalyst on MgO: Mononuclear Osmium Dicarbonyls formed from Os3(CO)12 Abstract: Supported triosmium clusters, formed from Os3(CO)12 on MgO, were treated in helium at 548 K for 2 h, causing fragmentation of the cluster frame and the formation of mononuclear osmium dicarbonyls. The cluster breakup and the resultant fragmented species were characterized by infrared and X-ray absorption spectroscopies, and the fragmented species were imaged by scanning transmission electron microscopy. The spectra identify the surface osmium complexes as Os(CO)2{Osupport}n (n = 3 or 4) (where the braces denote support surface atoms). The images show site-isolated Os atoms in mononuclear osmium species on MgO. The intensity analysis on the images of the MgO(110) face showed that the Os atoms were located atop Mg columns. This information led to a model of the Os(CO)2 on MgO(110), with the distances approximated as those determined by EXAFS spectroscopy, which are an average over the whole MgO surface; the results imply that these complexes were located at Mg vacancies.

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