Manipulating light–matter interaction in a gold nanorod assembly by plasmonic coupling

The interaction of light with a single gold nanorod (GNR) depends strongly on the polarization and wavelength of the light. For isolated GNRs, the maximum of the polarization (wavelength)‐dependent linear and nonlinear absorption appear at the same excitation polarization (wavelength). Here, it is demonstrated that these relationships can be manipulated in a GNR assembly composed of randomly distributed and oriented GNRs by controlling the plasmonic coupling strength between GNRs. It is revealed that the strongly localized modes resulting from the plasmonic coupling of GNRs play a crucial role in determining these relationships. For a GNR tetramer, it is shown by numerical simulation that the maximum two‐photon absorption achieved at a particular polarization can be switched to the minimum absorption and vice versa by controlling the coupling strength. More importantly, it is demonstrated both numerically and experimentally that the two‐photon‐absorption peak of a GNR assembly can be made to be different from its single‐photon‐absorption peak by increasing the coupling strength. Both properties are distinct from previous experimental observations. Our findings provide a useful guideline for engineering the interaction of light with complex plasmonic systems.

     

Mid‐infrared supercontinuum covering 2.0–16 μm in a low‐loss telluride single‐mode fiber

A mid‐infrared (MIR) supercontinuum (SC) has been demonstrated in a low‐loss telluride glass fiber. The double‐cladding fiber, fabricated using a novel extrusion method, exhibits excellent transmission at 8–14 μm: < 10 dB/m in the range of 8–13.5 μm and 6 dB/m at 11 μm. Launched intense ultrashort pulsed with a central wavelength of 7 μm, the step‐index fiber generates a MIR SC spanning from ∼2.0 μm to 16 μm, for a 40‐dB spectral flatness. This is a fresh experimental demonstration to reveal that telluride glass fiber can emit across the all MIR molecular fingerprint region, which is of key importance for applications such as diagnostics, gas sensing, and greenhouse CO₂ detection.

     

Electron–phonon coupling and vibrational modes contributing to linear electro‐optic effect of the efficient NLO chromophore 4‐(N,N‐dimethylamino)‐N‐methyl‐4′‐toluene sulfonate (DAST) from their vibrational spectra

The optimized geometry and structural features of the most prospective electro‐optic crystal 4‐(N,N‐dimethylamino)‐N‐methyl‐4′‐toluene sulfonate (DAST), and the vibrational spectral investigations have been comprehensively described with the near infrared Fourier transform (NIR FT) Raman and Fourier transform infrared (FT‐IR) spectra supported by the density functional theoretical (DFT) computations to elucidate the contribution of vibrational modes to the linear electro‐optic (LEO) effect. Mulliken population analysis and natural bond orbital (NBO) analysis have also been carried out to analyze the effects of intramolecular charge transfer (ICT), intramolecular hydrogen bonding and hyperconjugative interactions on the geometries. The influence of CT interaction between the phenyl ring and the dimethylamino group of the nonlinear optical (NLO) chromophore on the endocyclic and exocyclic angles, and the electronic effects such as hyperconjugation and back‐donation on the methyl hydrogen atoms have been examined. The concurrent intense activation of Raman and IR activities of the effective conjugation vibrational coordinate, which significantly contributes to the LEO effect resulting from the strong electron–phonon (e/ph) coupling, has been analyzed in detail. The effects of frontier orbitals, highest occupied molecular orbital (HOMO) and lowest unoccupied molecular orbital (LUMO), transition of electron density (ED) transfer and the influence of planarity in the stilbazolium ring on the first hyperpolarizability are also discussed. Copyright © 2008 John Wiley & Sons, Ltd.     

Topological Phase Transition and Eigenstates Localization in a Generalized Non‐Hermitian Su–Schrieffer–Heeger Model

The topological properties of a generalized non‐Hermitian Su–Schrieffer–Heeger model are investigated and it is demonstrated that the non‐Hermitian phase transition and the non‐Hermitian skin effect can be induced by intra‐cell asymmetric coupling under open boundary conditions. Through investigating and calculating the non‐Hermitian winding number with generalized Brillouin zone theory, it is found that the present non‐Hermitian system has an exact bulk‐boundary correspondence relationship. Meanwhile, the non‐Hermitian winding number is used to characterize the non‐Hermitian phase transition and determine the phase transition boundary, and it is found that the non‐Hermitian phase transition is not completely induced by the asymmetric coupling strength. By means of the mean inverse participation ratio, the factors that affect the eigenstates localization are shown and it is revealed that large system size or large asymmetric coupling strength can leave the system in the localized state. Additionally, it is found that for the asymmetric coupling strength and the system size, the eigenstates localization is much more sensitive to the asymmetric coupling strength.     

Electronic and structural effects on the nonlinear optical behavior in π‐conjugated structure bis(4‐nitrophenyl) carbonate: a vibrational spectroscopic approach

Fourier transform (FT)‐Raman and infrared (IR) spectra of the nonlinear optical (NLO) material bis(4‐nitrophenyl) carbonate were recorded and analyzed. The geometry, first hyperpolarizability and harmonic vibrational wavenumbers were calculated with the help of Becke3–Lee–Yang–Parr density functional theory method. The detailed interpretation of the vibrational spectra was carried out with the aid of normal coordinate analysis following the scaled quantum mechanical force field methodology. The second‐order NLO properties of the molecule were studied by the Kurtz and Perry powder reflection technique. Stability of the molecule arising from hyperconjugative interactions leading to its NLO activity and charge delocalization were analyzed using natural bond orbital analysis. Copyright © 2010 John Wiley & Sons, Ltd.