Direct Dynamic Evidence of Charge Separation in a Dye‐Sensitized Solar Cell Obtained under Operando Conditions by Raman Spectroscopy

Interfaces play an important role in enhancing the energy conversion performance of dye‐sensitized solar cells (DSCs). The interface effects have been studied by many techniques, but most of the studies only focused on one part of a DSC, rather than on a complete solar cell. Hence, monitoring the interface evolution of a DSC is still very challenging. Here, in situ/operando resonance Raman (RR) spectroscopic analyses were carried out to monitor the dynamics of the photovoltaic conversion processes in a DSC. We observed the creation of new species (i.e., polyiodide and iodine aggregates) in the photosensitization process. We also obtained molecular‐scale dynamic evidence that the bands from the C=C and C=N bonds of 2,2′‐bipyridyl (bpy), the S=C=N bonds of the NCS ligand, and photochemical products undergo reasonably strong intensity and frequency changes, which clearly demonstrates that they are involved in charge separation. Furthermore, RR spectroscopy can also be used to quickly evaluate the performance of DSCs.     

One-dimensional photonic crystal design

In this article we present a method to determine the band spectrum, band gaps, and discrete energy levels, of a one-dimensional photonic crystal with localized impurities. For one-dimensional crystals with piecewise constant refractive indices we develop an algorithm to recover the refractive index distribution from the period map. Finally, we derive the relationship between the period map and the scattering matrix containing the information on the localized modes.     

Polar decompositions and related classes of operators in spaces ∏κ

Polar decompositions with respect to an indefinite inner product are studied for bounded linear operators acting on a space. Criteria are given for existence of various forms of the polar decompositions, under the conditions that the range of a given operatorX is closed and that zero is not an irregular critical point of the selfadjoint operatorX ^[*]X. Both real and complex spaces are considered. Relevant classes of operators having a selfadjoint (in the sense of the indefinite inner product) square root, or a selfadjoint logarithm, are characterized.The work of this author was partially supported by INdAM-GNCS and MURSTThe work of this author was partially supported by NSF grant DMS-9988579.     

First-principles study of aqueous hydroxide solutions

Car-Parrinello molecular dynamics simulations have been carried out for aqueous NaOH and KOH solutions under ambient conditions over a wide range of concentrations. From these simulations, we have observed a continuous change of the water structure with added hydroxide, characterized by a significant shift of the second peak of the OO radial distribution functions to shorter distances. At the highest concentration investigated, the normal tetrahedral coordination of pure water is completely missing, a result that is consistent with a recent neutron diffraction experiment. The added hydroxide also gives rise to some unique spectroscopic features, including a "free" O-H stretch, a broadening of the normal water OH stretching band, and a large blue shift of both the librational band and the low-frequency translation. These results are in good agreement with the experimental data. Finally, it was demonstrated that the structural and dynamical behavior is inextricably linked to the formation of compact hydroxide-water complexes.     

Phenolic glycosides from the stem bark of Albizzia julibrissin

From the stem bark of Albizzia julibrissin DURAZZ (Leguminosae), two new phenolic glycosides (albibrissinosides A and B) were isolated. Their structures were determined by spectroscopic analysis. The albibrissinoside B was found to be a radical scavenger on the 1,1-diphenyl-2-picrylhydrazyl (DPPH) radical.     

Spectroscopic and Computational Insight into the Intermolecular Interactions between Zwitter‐Type Ionic Liquids and Water Molecules

Geometric and conformational changes of zwitter‐type ionic liquids (ZILs) due to hydrogen‐bonding interactions with water molecules are investigated by density functional theory (DFT), two‐dimensional IR correlation spectroscopy (2D IR COS), and pulsed‐gradient spin‐echo NMR (PGSE NMR). Simulation results indicate that molecular structures in the optimized states are strongly influenced by hydrogen bonding of water molecules with the sulfonate group or imidazolium and pyrrolidinium rings of 3‐(1‐methyl‐3‐imidazolio)propanesulfonate ( 1 ) and 3‐(1‐methyl‐1‐pyrrolidinio)propanesulfonate ( 2 ), respectively. Concentration‐dependent 2D IR COS reveals kinetic conformational changes of the two ZIL–H₂O systems attributable to intermolecular interactions, as well as the interactions of sulfonate groups and imidazolium or pyrrolidinium rings with water molecules. The dramatic changes in the ¹H self‐diffusion coefficients elucidate the formation of proton‐conduction pathways consisting of ZIL networks. In ZIL domains, protons are transferred by a Grotthuss‐type mechanism through formation, breaking, and restructuring of bonds between ZILs and H₂O, leading to an energetically favorable state. The simulation and experimental investigations delineated herein provide a perspective to understanding the interactions with water from an academic point of view as well as to designing ILs with desired properties from the viewpoint of applications.     

Understanding the Structural Differences between Spherical and Rod‐Shaped Human Insulin Nanoparticles Produced by Supercritical Fluids Precipitation

In this study, the thermal denaturation mechanism and secondary structures of two types of human insulin nanoparticles produced by a process of solution‐enhanced dispersion by supercritical fluids using dimethyl sulfoxide (DMSO) and ethanol (EtOH) solutions of insulin are investigated using spectroscopic approaches and molecular dynamics calculations. First, the temperature‐dependent IR spectra of spherical and rod‐shaped insulin nanoparticles prepared from DMSO and EtOH solution, respectively, are analyzed using principal component analysis (PCA) and 2D correlation spectroscopy to obtain a deeper understanding of the molecular structures and thermal behavior of the two insulin particle shapes. All‐atom molecular dynamics (AAMD) calculations are performed to investigate the influence of the solvent molecules on the production of the insulin nanoparticles and to elucidate the geometric differences between the two types of nanoparticles. The results of the PCA, the 2D correlation spectroscopic analysis, and the AAMD calculations clearly reveal that the thermal denaturation mechanisms and the degrees of hydrogen bonding in the spherical and rod‐shaped insulin nanoparticles are different. The polarity of the solvent might not alter the structure or function of the insulin produced, but the solvent polarity does influence the synthesis of different shapes of insulin nanoparticles.     

Background oriented schlieren for flow visualisation in hypersonic impulse facilities

Experiments to demonstrate the use of the background-oriented schlieren (BOS) technique in hypersonic impulse facilities are reported. BOS uses a simple optical set-up consisting of a structured background pattern, an electronic camera with a high shutter speed and a high intensity light source. The visualization technique is demonstrated in a small reflected shock tunnel with a Mach 4 conical nozzle, nozzle supply pressure of 2.2 MPa and nozzle supply enthalpy of 1.8 MJ/kg. A 20° sharp circular cone and a model of the MUSES-C re-entry body were tested. Images captured were processed using PIV-style image analysis to visualize variations in the density field. The shock angle on the cone measured from the BOS images agreed with theoretical calculations to within 0.5°. Shock standoff distances could be measured from the BOS image for the re-entry body. Preliminary experiments are also reported in higher enthalpy facilities where flow luminosity can interfere with imaging of the background pattern. A version of this paper was presented at the 25th International Symposium on Shock Waves in Bangalore in July 2005.