@article{KulikovskyNeherMecheretal.2004, author = {Kulikovsky, Lazar and Neher, Dieter and Mecher, E. and Meerholz, Klaus and Horhold, H. H. and Ostroverkhova, O.}, title = {Photocurrent dynamics in a poly(phenylene vinylene)-based photorefractive composite}, issn = {1098-0121}, year = {2004}, abstract = {All parameters describing the charge carrier dynamics in a poly(phenylene vinylene)-based photorefractive (PR) composite relevant to PR grating dynamics were determined using photoconductivity studies under various illumination conditions. In particular, the values of the coefficients for trap filling and recombination of charges with ionized sensitizer molecules could be extracted independently. It is concluded that the PR growth time without preillumination is mostly determined by the competition between deep trap filling and recombination with ionized sensitizer molecules. Further, the pronounced increase in PR speed upon homogeneous preillumination (gating) as reported recently is quantitatively explained by deep trap filling}, language = {en} } @article{BommerAbrahamsonStrasseretal.2004, author = {Bommer, Julian J. and Abrahamson, Norman A. and Strasser, F. O. and Pecker, Alain and Bard, Pierre-Yves and Bungum, Hilmar and Cotton, Fabrice and F{\"a}h, Donat and Sabetta, F. and Scherbaum, Frank and Studer, Jost}, title = {The challenge of defining upper bounds on earthquake ground motions}, issn = {0895-0695}, year = {2004}, language = {en} } @article{ZentelBehlNeheretal.2004, author = {Zentel, Rudolf and Behl, Marc and Neher, Dieter and Zen, Achmad and Lucht, Sylvia}, title = {Nanostructured polytriarylamines : orientation layers for polyfluorene}, issn = {0065-7727}, year = {2004}, language = {en} } @article{ScherbaumCottonSmit2004, author = {Scherbaum, Frank and Cotton, Fabrice and Smit, P.}, title = {On the use of response spectral-reference data for the selection and ranking of ground-motion models for seismic-hazard analysis in regions of moderate seismicity : the case of rock motion}, issn = {0037-1106}, year = {2004}, abstract = {The use of ground-motion-prediction equations to estimate ground shaking has become a very popular approach for seismic-hazard assessment, especially in the framework of a logic-tree approach. Owing to the large number of existing published ground-motion models, however, the selection and ranking of appropriate models for a particular target area often pose serious practical problems. Here we show how observed around-motion records can help to guide this process in a systematic and comprehensible way. A key element in this context is a new, likelihood based, goodness-of-fit measure that has the property not only to quantify the model fit but also to measure in some degree how well the underlying statistical model assumptions are met. By design, this measure naturally scales between 0 and 1, with a value of 0.5 for a situation in which the model perfectly matches the sample distribution both in terms of mean and standard deviation. We have used it in combination with other goodness-of-fit measures to derive a simple classification scheme to quantify how well a candidate ground-rnotion-prediction equation models a particular set of observed-response spectra. This scheme is demonstrated to perform well in recognizing a number of popular ground-motion models from their rock-site- recording, subsets. This indicates its potential for aiding the assignment of logic-tree weights in a consistent and reproducible way. We have applied our scheme to the border region of France, Germany, and Switzerland where the M-w 4.8 St. Die earthquake of 22 February 2003 in eastern France recently provided a small set of observed-response spectra. These records are best modeled by the ground-motion-prediction equation of Berge-Thierry et al. (2003), which is based on the analysis of predominantly European data. The fact that the Swiss model of Bay et al. (2003) is not able to model the observed records in an acceptable way may indicate general problems arising from the use of weak-motion data for strong-motion prediction}, language = {en} } @article{ScherbaumSchmedesCotton2004, author = {Scherbaum, Frank and Schmedes, J. and Cotton, Fabrice}, title = {On the conversion of source-to-site distance measures for extended earthquake source models}, issn = {0037-1106}, year = {2004}, abstract = {One of the major challenges in engineering seismology is the reliable prediction of site-specific ground motion for particular earthquakes, observed at specific distances. For larger events, a special problem arises, at short distances, with the source-to-site distance measure, because distance metrics based on a point-source model are no longer appropriate. As a consequence, different attenuation relations differ in the distance metric that they use. In addition to being a source of confusion, this causes problems to quantitatively compare or combine different ground- motion models; for example, in the context of Probabilistic Seismic Hazard Assessment, in cases where ground-motion models with different distance metrics occupy neighboring branches of a logic tree. In such a situation, very crude assumptions about source sizes and orientations often have to be used to be able to derive an estimate of the particular metric required. Even if this solves the problem of providing a number to put into the attenuation relation, a serious problem remains. When converting distance measures, the corresponding uncertainties map onto the estimated ground motions according to the laws of error propagation. To make matters worse, conversion of distance metrics can cause the uncertainties of the adapted ground-motion model to become magnitude and distance dependent, even if they are not in the original relation. To be able to treat this problem quantitatively, the variability increase caused by the distance metric conversion has to be quantified. For this purpose, we have used well established scaling laws to determine explicit distance conversion relations using regression analysis on simulated data. We demonstrate that, for all practical purposes, most popular distance metrics can be related to the Joyner-Boore distance using models based on gamma distributions to express the shape of some "residual function." The functional forms are magnitude and distance dependent and are expressed as polynomials. We compare the performance of these relations with manually derived individual distance estimates for the Landers, the Imperial Valley, and the Chi-Chi earthquakes}, language = {en} } @article{StillerKarageorgievGeueetal.2004, author = {Stiller, Burkhard and Karageorgiev, Peter and Geue, Thomas and Morawetz, Knut and Saphiannikova, Marina and Mechau, Norman and Neher, Dieter}, title = {Optically induced mass transport studied by scanning near-field optical- and atomic force microscopy}, issn = {0204-3467}, year = {2004}, abstract = {Some functionalised thin organic films show a very unusual property, namely the light induced material transport. This effect enables to generate three-dimensional structures on surfaces of azobenzene containing films only caused by special optical excitation. The physical mechanisms underlying this phenomenon have not yet been fully understood, and in addition, the dimensions of structures created in that way are macroscopic because of the optical techniques and the wavelength of the used light. In order to gain deeper insight into the physical fundamentals of this phenomenon and to open possibilities for applications it is necessary to create and study structures not only in a macroscopic but also in nanometer range. We first report about experiments to generate optically induced nano structures even down to 100 nm size. The optical stimulation was therefore made by a Scanning Near-field Optical Microscope (SNOM). Secondly, physical conditions inside optically generated surface relief gratings were studied by measuring mechanical properties with high lateral resolution via pulse force mode and force distance curves of an AFM}, language = {en} } @article{YangNeher2004, author = {Yang, X. H. and Neher, Dieter}, title = {Polymer electrophosphorescence devices with high power conversion efficiencies}, issn = {0003-6951}, year = {2004}, abstract = {We demonstrate efficient single-layer polymer phosphorescent light-emitting devices based on a green-emitting iridium complex and a polymer host co-doped with electron-transporting and hole-transporting molecules. These devices can be operated at relatively low voltages, resulting in a power conversion efficiency of up to 24 lm/W at luminous efficiencies exceeding 30 cd/A. The overall performances of these devices suggest that efficient electrophosphorescent devices with acceptable operating voltages can be achieved in very simple device structures fabricated by spin coating. (C) 2004 American Institute of Physics}, language = {en} } @article{YangNeherHerteletal.2004, author = {Yang, X. H. and Neher, Dieter and Hertel, D. and Daubler, T. K.}, title = {Highly efficient single-layer polymer electrophosphorescent devices}, issn = {0935-9648}, year = {2004}, abstract = {A commercially available Ir complex has been employed for the preparation of highly efficient (see Figure) single-layer phosphorescent polymer light,emitting diodes by use of appropriate thermal treatment and proper adjustment of the layer composition. These devices exhibit essentially no dependence of the driving field on the concentration of the Ir complex, suggesting that the build-up of space-charge in the layer is insignificant}, language = {en} } @article{HeydenreichKochKovacsetal.2004, author = {Heydenreich, Matthias and Koch, Andreas and Kovacs, J. and Toth, G. and Kleinpeter, Erich}, title = {Electronic influences on (3)J(C,H) coupling constants via -S-, -S(O)- and -SO2--: their determination, calculation and comparison of detection methods}, issn = {0749-1581}, year = {2004}, abstract = {(3)J(C,H) coupling constants via a sulfur atom in two series of compounds, both including a sulfide, a sulfoxide and a sulfone, were detected experimentally and calculated by quantum mechanical methods. In the first series (1-3) the coupling between a hydrogen, bonded to an Sp(3) carbon, and an Sp(2) carbon is treated; the second series (4- 6) deals with the coupling between a hydrogen, bonded to an Sp3 carbon, and an Sp3 carbon. Different pulse sequences (broadband HMBC, SelJres, 1D HSQMBC, J-HMBC-2, selective J-resolved long-range experiment and IMPEACH-MBC) proved to be useful in determining the long-range (3)J(C,H) coupling constants. However, the dynamic behaviour of two of the compounds (4 and 6) led to weighted averages of the two coupling constants expected (concerning equatorial and axial positions of the corresponding hydrogens). DFT calculations proved to be useful to calculate not only the (3)J(C,H) coupling constants but also the different contributions of FC, PSO, DSO and SD terms; the calculation of the Fermi contact term (FC) was found to be sufficient for the correct estimation of (3)J(C,H) coupling constants. Copyright (C) 2004 John Wiley Sons, Ltd}, language = {en} } @article{HeydenreichWolfWolleretal.2004, author = {Heydenreich, Matthias and Wolf, G. and Woller, Jochen and Kleinpeter, Erich}, title = {Restricted rotation of the amino group and ring inversion in highly substituted anilines. A dynamic NMR and computational study}, issn = {0040-4020}, year = {2004}, abstract = {The reaction of cyclic ylidene malononitriles with acetylene (di)carboxylic acid esters led to the production of nine bicyclic systems incorporating highly substituted (5/6) anilines. The free energy of activation (DeltaG(\#)) for the restricted rotation about the aniline-NH2 bond was experimentally measured in each case and a correlation was evident between the increase in steric strain in the ground state, the electron withdrawing capabilities of the ring substituents, and a reduction in the rotational barrier. For four of the compounds, the slow ring interconversion (chairreversible arrowchair) for the annelated saturated seven-membered ring that formed part of the bicyclic system was also evident. In these four compounds, both dynamic processes were also studied theoretically using ab initio methods whilst the ring interconversion was additionally studied using molecular dynamic simulations. The interconversion between the two stable chair forms was deemed to occur via a conformation series consisting of chairreversible arrowboatreversible arrowtwist-boatreversible arrowboatreversible arrowchair. (C) 2004 Elsevier Ltd. All rights reserved}, language = {en} } @article{KleinpeterKlod2004, author = {Kleinpeter, Erich and Klod, Sabrina}, title = {Separation of anisotropic and steric substituent effects - nuclear chemical shielding analysis of H-4 and C-4 in phenanthrene and 11-ethynylphenanthrene}, year = {2004}, abstract = {The anisotropic effect of a proximally introduced ethynyl group on the chemical shifts of H-4 and C-4 of the phenanthrene skeleton was calculated using GIAO-HF/NICS methodology. The anisotropic effect, long considered to be the source of the considerable downfield shift of H-4 in 11-ethynylphenanthrene in comparison to the chemical shift value of the corresponding proton in phenanthrene, was determined to be only negligible in magnitude on the basis of these calculations. Partitioning of the natural chemical shieldings of H-4 and C-4 by the NCS-NBO method into various contributions from the C-C and C-H bonds present in each molecule revealed that steric compression was able to account for the large downfield shifts of both H-4 and C-4 in 11-ethynylphenanthrene relative to phenanthrene. Thus, the substituent effect is almost totally permeated by this latter interaction and not by the aforementioned process, which was previously presumed to be the sole underlying cause}, language = {en} } @article{KoetzGuentherKosmellaetal.2004, author = {Koetz, Joachim and G{\"u}nther, Claudia and Kosmella, Sabine and Kleinpeter, Erich and Wolf, Gunter}, title = {Polyelectrolyte induced structural changes in the isotropic phase of the system sulfobetaine/pentanol/toluene/ water}, year = {2004}, language = {en} } @article{TewsBlaumJeltsch2004, author = {Tews, J{\"o}rg and Blaum, Niels and Jeltsch, Florian}, title = {Structural and animal species diversity in arid and semi-arid savannas of the southern Kalahari}, year = {2004}, language = {en} } @article{KleinpeterKlodRudorf2004, author = {Kleinpeter, Erich and Klod, Sabrina and Rudorf, Wolf-Dieter}, title = {Electronic state of push-pull alkenes : an experimental dynamic NMR and theoretical ab initio MO study}, year = {2004}, abstract = {The H-1 and C-13 NMR spectra of a number of push-pull alkenes were recorded and the C-13 chemical shifts calculated employing the GIAO perturbation method. Of the various levels of theory tried, MP2 calculations with a triple- zeta-valence basis set were found to be the most effective for providing reliable results. The effect of the solvent was also considered but only by single-point calculations. Generally, the agreement between the experimental and theoretically calculated C-13 chemical shifts was good with only the carbons of the carbonyl, thiocarbonyl, and cyano groups deviating significantly. The substituents on the different sides of the central C=C partial double bond were classified qualitatively with respect to their donor (S,S < S,N < N,N) and acceptor properties (CdropN < C=O < C=S) and according to the ring size on the donor side (6 < 7 < 5). The geometries of both the ground (GS) and transition states (TS) of the restricted rotation about the central C=C partial double bond were also calculated at the HF and MP2 levels of theory and the free energy differences compared with the barriers to rotation determined experimentally by dynamic NMR spectroscopy. Structural differences between the various push-pull alkenes were reproduced well, but the barriers to rotation were generally overestimated theoretically. Nevertheless, by correlating the barriers to rotation and the length of the central C=C partial double bonds, the push-pull alkenes could be classified with respect to the amount of hydrogen bonding present, the extent of donor-acceptor interactions (the push-pull effect), and the level of steric hindrance within the molecules. Finally, by means of NBO analysis of a set of model push-pull alkenes (acceptors: - CdropN, -CH=O, and -CH=S; donors: S, O, and NH), the occupation numbers of the bonding pi orbitals of the central C=C partial double bond were shown to quantitatively describe the acceptor powers of the substituents and the corresponding occupation numbers of the antibonding pi* orbital the donor powers of the substituents. Thus, for the first time an estimation of both the acceptor and the donor properties of the substituents attached to the push-pull double bond have been separately quantified. Furthermore, both the balance between strong donor/weak acceptor substituents (and vice versa) and the additional influences on the barriers to rotation (hydrogen bonding and steric hindrance in the GSs and TSs) could be differentiated}, language = {en} } @article{KleinpeterSeidl2004, author = {Kleinpeter, Erich and Seidl, Peter Rudolf}, title = {The gamma- and the delta-effects in C-13 NMR spectroscopy in terms of nuclear chemical shielding (NCS) analysis}, year = {2004}, abstract = {Carbon-13 NMR is widely used in the determination of the stereochemistry of organic compounds. Changes in chemical shifts caused by interactions of groups that are close in space normally result in shielding of the carbon and deshielding of the hydrogen nuclei that are involved. This is not always the case, however, and further work on the origin of these effects would be desirable. Early applications of theoretical methods to the study of NMR shielding parameters were not particularly successful, but in recent years, the calculation of NMR shielding parameters by theoretical methods has developed into a useful and popular tool for structural studies by NMR. A promising approach to the problem of distinguishing and evaluating stereochemical influences on carbon and hydrogen chemical shifts is provided by natural chemical shielding (NCS) analysis. This method allows a partitioning of theoretical NMR shieldings into magnetic contributions from bonds and lone pairs of the molecule using the natural bond orbital (NBO) method. In order to investigate the origins of steric effects, we employed the NCS analysis to axial/equatorial-Me-cyclohexane, norbornane and exo/endo-Me-norbornane, in addition to n-pentane in the anti, gauche and g(P) g(M) conformations. Our results indicate that distortions in molecular structure due to steric effects can result in bond stretching or compression or in angular distortions. Changes in bond lengths result in the predictable shielding or deshielding of the nuclei that are involved. Where the molecular framework may be distorted to alleviate strain, chemical shifts appear to reflect changes in angles. Copyright (C) 2004 John Wiley Sons, Ltd}, language = {en} } @article{HolzbergerHoldtKleinpeter2004, author = {Holzberger, Anja and Holdt, Hans-J{\"u}rgen and Kleinpeter, Erich}, title = {Conformational analysis of mixed oxathia crown ethers and their complexational ability towards Ag(I) and Pd(II) : an experimental solution NMR and theoretical molecular modelling study}, issn = {1477-0520}, year = {2004}, abstract = {Both the conformation and flexibility of four mixed oxathia crown ethers and their Ag(I) and Pd(II) complexes were studied by H-1 NMR (delta, J, NOE, T-1), C-13 NMR, dynamic 1H NMR spectroscopy and molecular modelling. The stoichiometry and stability constants of the complexes were determined from corresponding Job's plots in the case of Ag(I) complexes as the interchange between free and complexed states was fast on the NMR timescale; interchange for the Pd(II) complexes was sufficiently slow such that distinct sub-spectra were observable for the free and complexed states. In all cases where complexation was observed, 1 : 1 complexes were formed. Global minima structures determined from the modelling studies were analysed with respect to the barriers to ring interconversion, the flexibility of the species in solution and the preferred complexation of Ag(I) and Pd(II) to the sulfur atoms of the crown ethers}, language = {en} } @article{KleinpeterKlod2004, author = {Kleinpeter, Erich and Klod, Sabrina}, title = {Ab initio calculation of the anisotropic/ring current effects of amino acid residues to locate the position of substrates in the binding site of enzymes}, year = {2004}, abstract = {The ring current effects of aromatic moieties and the anisotropic effects of the C=O and C-X (X = C, N, S) bonds and of the NH=C(NH2)-NH- moiety in the side chains of amino acid residues of proteins were ab initio calculated based on nuclear independent chemical shieldings as employed by P.v.R. Schleyer. Hereby, quantitative information about the spatial extension, sign and scope of the corresponding ring current/anisotropic effects was obtained and they were visualized as iso-chemical-shielding-surfaces. Examining this quantitative information compared with experimental NMR chemical shifts, the role of the corresponding amino acid residues in binding substrates in the binding site of enzymes was studied. (C) 2004 Elsevier B.V. All rights reserved}, language = {en} } @article{HolzbergerKleinpeter2004, author = {Holzberger, Anja and Kleinpeter, Erich}, title = {Solution structure of the palladium(II) complex of 1,4,7,10-tetrathiacyclododec-2-ene-2,3-dicarbonitrile}, issn = {0749-1581}, year = {2004}, abstract = {The solution structure of the Pd(II) complex of mn-12-S-4 was studied in detail by NMR spectroscopy. The stoichiometry of the complex was determined by H-1 NMR titration experiments. (3)J(H,H) coupling constants were extracted from the 2D J-resolved NMR spectrum of the complex providing information concerning the S-C-C-S torsional angles. Further conclusions about the conformation of [Pd(mn-12-S-4)](BF4)(2) were drawn from experimental NOES. The results of the NMR study were corroborated by molecular modelling. Copyright (C) 2004 John Wiley Sons, Ltd}, language = {en} } @article{HolzbergerHoldtKleinpeter2004, author = {Holzberger, Anja and Holdt, H. N. and Kleinpeter, Erich}, title = {NMR spectroscopic and molecular modelling study of the solution structure and the complexational behavior of maleonitrile tetrathia crown ethers with silver(I)}, year = {2004}, abstract = {The flexibility and complex formation of two maleonitrile tetrathia crown ethers were studied in solution using H-1 and C-13 NMR spectroscopy and molecular modelling. Both the stoichiometry and the stability of the complexes that these crown ethers form with Ag(I) were determined by NMR titration measurements. Spin-lattice relaxation time measurements provided information concerning the donor atoms involved in complex formation and also the intramolecular mobility of the free and complexed ligands. Molecular modelling was also used to gain further insight into the conformational space of the free ligands and their silver(I) complexes. Copyright (C) 2004 John Wiley Sons, Ltd}, language = {en} } @article{KochMikhovaKleinpeter2004, author = {Koch, Andreas and Mikhova, Bozhana and Kleinpeter, Erich}, title = {Ab initio MP2/GIAO/NBO study of the delta-syn-axial effect in C-13 NMR spectroscopy}, issn = {0022-2860}, year = {2004}, abstract = {The C-13 chemical shifts of 20 rigid bicyclic compounds have been calculated with ab initio HF and MP2 methods. The calculations showed very good reproducibility of the experimental values. The molecular orbital interactions in the rigid, nearly planar delta-syn-axial fragments in the isomeric groups of norbornane derivatives 1.x-4.x were studied in detail and were employed to explain the deshielding delta-syn-axial effect in C-13 NMR spectroscopy. (C) 2004 Elsevier B.V. All rights reserved}, language = {en} }