Average crossing number of Gaussian and equilateral chains with and without excluded volume

We study the influence of excluded volume interactions on the behaviour of the mean average crossing number (mACN) for random off-lattice walks. We investigated Gaussian and equilateral off-lattice random walks with and without ellipsoidal excluded volume up to chain lengths of N = 1500 and equilateral random walks on a cubic lattice up to N = 20000. We find that the excluded volume interactions have a strong influence on the behaviour of the local crossing number 〈 a(l₁,l₂) 〉 at very short distances but only a weak one at large distances. This behaviour is the basis of the proof in [ Y. Diao et al., Math. Gen. 36, 11561 (2003); Y. Diao and C. Ernst, Physical and Numerical Models in Knot Theory Including Applications to the Life Sciences] for the dependence of the mean average crossing number on the chain length N. We show that the data is compatible with an Nln(N)-bahaviour for the mACN, even in the case with excluded volume.     

Towards finite-dimensional gelation

We consider the gelation of particles which are permanently connected by random crosslinks, drawn from an ensemble of finite-dimensional continuum percolation. To average over the randomness, we apply the replica trick, and interpret the replicated and crosslink-averaged model as an effective molecular fluid. A Mayer-cluster expansion for moments of the local static density fluctuations is set up. The simplest non-trivial contribution to this series leads back to mean-field theory. The central quantity of mean-field theory is the distribution of localization lengths, which we compute for all connectivities. The highly crosslinked gel is characterized by a one-to-one correspondence of connectivity and localization length. Taking into account higher contributions in the Mayer-cluster expansion, systematic corrections to mean-field can be included. The sol-gel transition shifts to a higher number of crosslinks per particle, as more compact structures are favored. The critical behavior of the model remains unchanged as long as finite truncations of the cluster expansion are considered. To complete the picture, we also discuss various geometrical properties of the crosslink network, e.g. connectivity correlations, and relate the studied crosslink ensemble to a wider class of ensembles, including the Deam-Edwards distribution. Received on 24 April 2002 Published online 14 October 2002 RID="a" ID="a"deceased RID="b" ID="b"e-mail: weigt@theorie.physik.uni-goettingen.de     

Spectrally selective organic photodiodes

We report on the fabrication of spectrally selective organic photodiodes (OPDs) and present a green sensitive OPD, whose spectral response peaks in the green region between 470 nm and 560 nm, as well as a red sensitive OPD whose spectral response peaks in the red region between 610 nm to 720 nm. We show that the spectral sensitivity of OPDs can be tuned by either choosing organic semiconductors with the appropriate photoresponse or by utilizing adequate device architectures with integrated optical filters. The results demonstrate the great flexibility of organic semiconductor materials. (© 2008 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

A fullerene silirane derivative to improve the open circuit voltage in a polymer–fullerene solar cell: a theoretical study

In this letter quantum chemical calculations are performed on fullerene derivatives with varying reduction potentials, successfully used as electron acceptor in bulk heterojunction solar cells with the aim to investigate the energy levels of the frontier orbitals. We have successfully correlated the theoretical lowest unoccupied molecular orbital (LUMO) levels of different fullerenes with the open circuit voltage of the photovoltaic device based on the polymer–fullerene blend. We have also proposed a new fullerene silirane derivative with a raised LUMO level useful to increase the open circuit voltage of a polymer solar cell. (© 2008 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Experimental Studies on the Response of the Fiber Optic Evanescent Field Absorption Sensor

In the present study the response of the fiber optic evanescent field absorption sensor has been analyzed experimentally. The dependence of evanescent absorbance on sample (dye) concentration has been found to be nonlinear, in contradiction to theoretical predictions. The amount of nonlinearity as well as evanescent absorbance has been found to depend on the pH of the sample. As the pH decreases, the amount of nonlinearity and evanescent absorbance decrease. It has been shown that the nonlinearity and high evanescent absorbance at high pH value occur because of the adsorption of the positively charged dye molecules on the surface of the silica core of the plastic-clad silica (PCS) fiber, which is generally used for the sensor. A linear response has been obtained at pH close to 2.0, at which the presence of a tremendous amount of H ions in the sample restricts the adsorption of the dye molecules. The following empirical relation has been found to fit the experimental data: gamma 1.1C 1.6(pH)32C 1 3, where gamma is the evanescent absorption coefficient and C is the concentration of the dye. The first term is due to the simple Beer's law while the second term is the contribution of the pH dependent dye adsorption. In addition, we have found that the increase in core diameter increases the contribution of adsorption.     

The effect of oxygen exposure on pentacene electronic structure

We use ultraviolet photoelectron spectroscopy to investigate the effect of oxygen and air exposure on the electronic structure of pentacene single crystals and thin films. It is found that O₂ and water do not react noticeably with pentacene, whereas singlet oxygen/ozone readily oxidize the organic compound. Also, we obtain no evidence for considerable p-type doping of pentacene by O₂ at low pressure. However, oxygen exposure lowers the hole injection barrier at the interface between Au and pentacene by 0.25 eV, presumably due to a modification of the Au surface properties.     

Viscoelastic characterization of compacted pharmaceutical excipient materials by analysis of frequency-dependent mechanical relaxation processes

A newly developed method for determining the frequency-dependent complex Young's modulus was employed to analyze the mechanical response of compacted microcrystalline cellulose, sorbitol, ethyl cellulose and starch for frequencies up to 20 kHz. A Debye-like relaxation was observed in all the studied pharmaceutical excipient materials and a comparison with corresponding dielectric spectroscopy data was made. The location in frequency of the relaxation peak was shown to correlate to the measured tensile strength of the tablets, and the relaxation was interpreted as the vibrational response of the interparticle hydrogen and van der Waals bindings in the tablets. Further, the measured relaxation strength, holding information about the energy loss involved in the relaxation processes, showed that the weakest material in terms of tensile strength, starch, is the material among the four tested ones that is able to absorb the most energy within its structure when exposed to external perturbations inducing vibrations in the studied frequency range. The results indicate that mechanical relaxation analysis performed over relatively broad frequency ranges should be useful for predicting material properties of importance for the functionality of a material in applications such as, e.g., drug delivery, drug storage and handling, and also for clarifying the origin of hitherto unexplained molecular processes.     

Resonantly enhanced off-specular X-ray scattering from polymer/polymer interfaces<Superscript>⋆</Superscript>

We have used measurements of the absolute intensity of diffuse X-ray scattering to extract the interfacial tension of a buried polymer/polymer interface. Diffuse scattering was excited by an X-ray standing wave whose phase was adjusted to have a high intensity at the polymer/polymer interface and simultaneously a node at the polymer/air interface. This method permits the capillary-wave-induced roughness of the interface, and hence the interfacial tension, to be measured independently of the polymer/polymer interdiffusion.     

Correlation between the Soret coefficient and the static structure factor in a polymer blend

Mutual mass diffusion and thermal diffusion has been investigated in poly(dimethylsiloxane)/ poly(ethylmethylsiloxane) (PDMS/PEMS) polymer blends of equal weight fractions. Molar masses ranged from below 1 to over 20 kg/mol. Both the mutual mass (D) and the thermal diffusion (D_T) coefficient contain a thermally activated factor with an activation temperature of 1415 K. The molar mass dependence of D_T is due to an end-group effect of the local friction coefficient. The thermal diffusion coefficient in the limit of long chains and infinite temperature is D_T^0, = - 1.69×10^-7cm²(sK)^-1. The Soret coefficient S_T of blends far enough away from a critical point is proportional to the static structure factor S(q = 0).     

Effects of confinement on static and dynamical properties of water

Molecular-dynamics results on water confined in a silica pore are reviewed and discussed in connection with experiments performed on water in Vycor and with studies of water in contact with proteins. The properties of confined water are studied as a function of both temperature and hydration level. The interaction of water in the film close to the substrate with the silica atoms induces a strong distortion of the hydrogen bond network. At high hydration levels a double dynamical regime is observed. At low hydration an anomalous diffusion is found upon supercooling with a transition from a Brownian to a non-Brownian regime on approaching the substrate in agreement with results found in studies of water in contact with globular proteins.Received: 1 January 2003, Published online: 14 October 2003PACS: 61.20.-p Structure of liquids - 61.20.Ja Computer simulation of liquid structure