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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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