Charge transfer reactions in nematic liquid crystals

Ultrafast transient absorption studies of intramolecular photoinduced charge separation and thermal charge recombination were carried out on a molecule consisting of a 4-(N-pyrrolidino)naphthalene-1,8-imide donor (PNI) covalently attached to a pyromellitimide acceptor (PI) dissolved in the liquid crystal 4{prime}-(n-pentyl)-4-cyanobiphenyl (5CB). The temperature dependencies of the charge separation and recombination rates were obtained at temperatures above the nematic-isotropic phase transition of 5CB, where ordered microdomains exist and scattering of visible light by these domains is absent. The authors show that excited state charge separation is dominated by molecular reorientation of 5CB perpendicular to the director within the liquid crystal microdomains. They also show that charge recombination is adiabatic and is controlled by the comparatively slow collective reorientation of the liquid crystal microdomains relative to the orientation of PNI{sup +}-PI{sup {minus}}. They also report the results of time resolved electron paramagnetic resonance (TREPR) studies of photoinduced charge separation in a series of supramolecular compounds dissolved in oriented liquid crystal solvents. These studies permit the determination of the radical pair energy levels as the solvent reorganization energy increases from the low temperature crystalline phase, through the soft glass phase, to the nematic phase of the liquid crystal

Ultrafast Optical Modulation of Second- and Third-Harmonic Generation from Cut-Disk-Based Metasurfaces

We design and fabricate a metasurface composed of gold cut-disk resonators that exhibits a strong coherent nonlinear response. We experimentally demonstrate all-optical modulation of both second- and third-harmonic signals on a subpicosecond time scale. Pump−probe experiments and numerical models show that the observed effects are due to the ultrafast response of the electronic excitations in the metal under external illumination. These effects pave the way for the development of novel active nonlinear metasurfaces with controllable and switchable coherent nonlinear response

Mapping the Electromagnetic Near-Field Enhancements of Gold Nanocubes

International audienceWe imaged and quantitatively characterized electromagnetic hot spots near the surfaces of plasmon resonant gold nanocubes. The strongest fields are localized at the nanocube corners as compared to those on the sides. The near-field enhancement on the surface of the cube was imaged as a function of incident polarization, leading to information on the localization of fields on specific regions on the surface. We found that the field intensity drops dramatically when the nanocube corner is slightly tilted with respect to the incident laser polarization. This dramatic dependence on angle was verified by electrodynamics simulations. These results will enable the use of gold nanocubes in field enhancement applications and refractive-index sensing

Plasmon-based photopolymerization: near-field probing, advanced photonic nanostructures and nanophotochemistry

Cataloged from PDF version of article.Hybrid nanomaterials are targeted by a rapidly growing group of nanooptics researchers, due to the promise of optical behavior that is difficult or even impossible to create with nanostructures of homogeneous composition. Examples of important areas of interest include coherent coupling, Fano resonances, optical gain, solar energy conversion, photocatalysis, and nonlinear optical interactions. In addition to the coupling interactions, the strong dependence of optical resonances and damping on the size, shape, and composition of the building blocks provides promise that the coupling interactions of hybrid nanomaterials can be controlled and manipulated for a desired outcome. Great challenges remain in reliably synthesizing and characterizing hybrid nanomaterials for nanooptics. In this review, we describe the synthesis, characterization, and applications of hybrid nanomaterials created through plasmon-induced photopolymerization. The work is placed within the broader context of hybrid nanomaterials involving plasmonic metal nanoparticles and molecular materials placed within the length scale of the evanescent field from the metal surface. We specifically review three important applications of free radical photopolymerization to create hybrid nanoparticles: local field probing, photoinduced synthesis of advanced hybrid nanoparticles, and nanophotochemistry

Optical creation of vibrational intrinsic localized modes in anharmonic lattices with realistic interatomic potentials

Using an efficient optimal control scheme to determine the exciting fields, we theoretically demonstrate the optical creation of vibrational intrinsic localized modes (ILMs) in anharmonic perfect lattices with realistic interatomic potentials. For systems with finite size, we show that ILMs can be excited directly by applying a sequence of femtosecond visible laser pulses at THz repetition rates. For periodic lattices, ILMs can be created indirectly via decay of an unstable extended lattice mode which is excited optically either by a sequence of pulses as described above or by a single picosecond far-infrared laser pulse with linearly chirped frequency. In light of recent advances in experimental laser pulse shaping capabilities, the approach is experimentally promising.Comment: 20 pages, 7 eps figures. Accepted, Phys. Rev.