128 research outputs found
Insights into the Kinetics of Supramolecular Comonomer Incorporation in Water
Multicomponent supramolecular polymers are a versatile platform to prepare functional architectures, but a few studies have been devoted to investigate their noncovalent synthesis. Here, we study supramolecular copolymerizations by examining the mechanism and time scales associated with the incorporation of new monomers in benzene-1,3,5-tricarboxamide (BTA)-based supramolecular polymers. The BTA molecules in this study all contain three tetra(ethylene glycol) chains at the periphery for water solubility but differ in their alkyl chains that feature either 10, 12 or 13 methylene units. C(10)BTA does not form ordered supramolecular assemblies, whereas C(12)BTA and C(13)BTA both form high aspect ratio supramolecular polymers. First, we illustrate that C(10)BTA can mix into the supramolecular polymers based on either C(12)BTA or C(13)BTA by comparing the temperature response of the equilibrated mixtures to the temperature response of the individual components in water. Subsequently, we mix C(10)BTA with the polymers and follow the copolymerization over time with UV spectroscopy and hydrogen/deuterium exchange mass spectrometry experiments. Interestingly, the time scales obtained in both experiments reveal significant differences in the rates of copolymerization. Coarse-grained simulations are used to study the incorporation pathway and kinetics of the C(10)BTA monomers into the different polymers. The results demonstrate that the kinetic stability of the host supramolecular polymer controls the rate at which new monomers can enter the existing supramolecular polymers
Transformation Optics for Plasmonics
A new strategy to control the flow of surface plasmon polaritons at metallic
surfaces is presented. It is based on the application of the concept of
Transformation Optics to devise the optical parameters of the dielectric medium
placed on top of the metal surface. We describe the general methodology for the
design of Transformation-Optical devices for surface plasmons and analyze, for
proof-of-principle purposes, three representative examples with different
functionalities: a beam shifter, a cylindrical cloak and a ground-plane cloak.Comment: 15 pages, 3 figure
Surface electrons at plasma walls
In this chapter we introduce a microscopic modelling of the surplus electrons
on the plasma wall which complements the classical description of the plasma
sheath. First we introduce a model for the electron surface layer to study the
quasistationary electron distribution and the potential at an unbiased plasma
wall. Then we calculate sticking coefficients and desorption times for electron
trapping in the image states. Finally we study how surplus electrons affect
light scattering and how charge signatures offer the possibility of a novel
charge measurement for dust grains.Comment: To appear in Complex Plasmas: Scientific Challenges and Technological
Opportunities, Editors: M. Bonitz, K. Becker, J. Lopez and H. Thomse
Transformational Plasmon Optics
Transformation optics has recently attracted extensive interest, since it
provides a novel design methodology for manipulating light at will. Although
transformation optics in principle embraces all forms of electromagnetic
phenomena on all length scales, so far, much less efforts have been devoted to
near-field optical waves, such as surface plasmon polaritons (SPPs). Due to the
tight confinement and strong field enhancement, SPPs are widely used for
various purposes at the subwavelength scale. Taking advantage of transformation
optics, here we demonstrate that the confinement as well as propagation of SPPs
can be managed in a prescribed manner by careful control of the dielectric
material properties adjacent to a metal. Since the metal properties are
completely unaltered, it provides a straightforward way for practical
realizations. We show that our approach can assist to tightly bound SPPs over a
broad wavelength band at uneven and curved surfaces, where SPPs would normally
suffer significant scattering losses. In addition, a plasmonic waveguide bend
and a plasmonic Luneburg lens with practical designs are proposed. It is
expected that merging the unprecedented design flexibility based on
transformation optics with the unique optical properties of surface modes will
lead to a host of fascinating near-field optical phenomena and devices.Comment: 17 pages, 6 figure
Tuning the electronic properties of boron nitride nanotube by mechanical uni-axial deformation: a DFT study
The effect of uni-axial strain on the electronic properties of (8,0) zigzag and (5,5) armchair boron nitride nanotubes (BNNT) is addressed by density functional theory calculation. The stress-strain profiles indicate that these two BNNTS of differing types display very similar mechanical properties, but there are variations in HOMO-LUMO gaps at different strains, indicating that the electronic properties of BNNTs not only depend on uni-axial strain, but on BNNT type. The variations in nanotube geometries, partial density of states of B and N atoms, B and N charges are also discussed for (8,0) and (5,5) BNNTs at different strains
Low dimensional nanostructures of fast ion conducting lithium nitride
As the only stable binary compound formed between an alkali metal and nitrogen, lithium nitride possesses remarkable properties and is a model material for energy applications involving the transport of lithium ions. Following a materials design principle drawn from broad structural analogies to hexagonal graphene and boron nitride, we demonstrate that such low dimensional structures can also be formed from an s-block element and nitrogen. Both one- and two-dimensional nanostructures of lithium nitride, Li3N, can be grown despite the absence of an equivalent van der Waals gap. Lithium-ion diffusion is enhanced compared to the bulk compound, yielding materials with exceptional ionic mobility. Li3N demonstrates the conceptual assembly of ionic inorganic nanostructures from monolayers without the requirement of a van der Waals gap. Computational studies reveal an electronic structure mediated by the number of Li-N layers, with a transition from a bulk narrow-bandgap semiconductor to a metal at the nanoscale
Intermolecular singlet and triplet exciton transfer integrals from many-body Green's functions theory
A general approach to determine orientation and distance-dependent effective intermolecular exciton transfer integrals from many-body Green's functions theory is presented. On the basis of the GW approximation and the Bethe-Salpeter equation (BSE), a projection technique is employed to obtain the excitonic coupling by forming the expectation value of a supramolecular BSE Hamiltonian with electron-hole wave functions for excitations localized on two separated chromophores. Within this approach, accounting for the effects of coupling mediated by intermolecular charge transfer (CT) excitations is possible via perturbation theory or a reduction technique. Application to model configurations of pyrene dimers shows an accurate description of short-range exchange and long-range Coulomb interactions for the coupling of singlet and triplet excitons. Computational parameters, such as the choice of the exchange-correlation functional in the density-functional theory (DFT) calculations that underly the GW-BSE steps and the convergence with the number of included CT excitations, are scrutinized. Finally, an optimal strategy is derived for simulations of full large-scale morphologies by benchmarking various approximations using pairs of dicyanovinyl end-capped oligothiophenes (DCV5T), which are used as donor material in state-of-the-art organic solar cells
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