Anita Zeidler

Molecular Origins of Optoelectronic Properties in Coumarin Dyes: Toward Designer Solar Cell and Laser Applications

Coumarin derivatives are used in a wide range of applications, such as dye-sensitized solar cells (DSCs) and dye lasers, and have therefore attracted considerable research interest. In order to understand the molecular origins of their optoelectronic properties, molecular structures for 29 coumarin laser dyes are statistically analyzed. To this end, data for 25 compounds were taken from the Cambridge Structural Database and compared with data for four new crystal structures of coumarin laser dyes [Coumarin 487 (C(19)H(23)NO(2)), Coumarin 498 (C(16)H(17)NO(4)S), Coumarin 510 (C(20)H(18)N(2)O(2)), and Coumarin 525 (C(22)H(18)N(2)O(3))], which are reported herein. The competing contributions of different resonance states to the bond lengths of the 4- and 7-substituted coumarin laser dyes are computed based on the harmonic oscillator stabilization energy model. Consequently, a positive correlation between the contribution of the para-quinoidal resonance state and the UV-vis peak absorption wavelength of these coumarins is revealed. Furthermore, the perturbations of optoelectronic properties, owing to chemical substituents in these coumarin laser dyes, are analyzed: it is found that their UV-vis peak absorption and lasing wavelengths experience a red shift, as the electron-donating strength of the 7-position substituent increases and/or the electron-withdrawing strength of the 3- or 4-position substituent rises; this conclusion is corroborated by quantum-chemical calculations. It is also revealed that the closer the relevant substituents align with the direction of the intramolecular charge transfer (ICT), the larger the spectral shifts and the higher the molar extinction coefficients of coumarin laser dyes. These findings are important for understanding the ICT mechanism in coumarins. Meanwhile, all structure-property correlations revealed herein will enable knowledge-based molecular design of coumarins for dye lasers and DSC applications.

Networks under pressure: the development of in situ high-pressure neutron diffraction for glassy and liquid materials

The pressure-driven collapse in the structure of network-forming materials will be considered in the gigapascal (GPa) regime, where the development of in situ high-pressure neutron diffraction has enabled this technique to obtain new structural information. The improvements to the neutron diffraction methodology are discussed, and the complementary nature of the results is illustrated by considering the pressure-driven structural transformations for several key network-forming materials that have also been investigated by using other experimental techniques such as x-ray diffraction, inelastic x-ray scattering, x-ray absorption spectroscopy and Raman spectroscopy. A starting point is provided by the pressure-driven network collapse of the prototypical network-forming oxide glasses B2O3, SiO2 and GeO2. Here, the combined results help to show that the coordination number of network-forming structural motifs in a wide range of glassy and liquid oxide materials can be rationalised in terms of the oxygen-packing fraction over an extensive pressure and temperature range. The pressure-driven network collapse of the prototypical chalcogenide glass GeSe2 is also considered where, as for the case of glassy GeO2, site-specific structural information is now available from the method of in situ high-pressure neutron diffraction with isotope substitution. The application of in situ high-pressure neutron diffraction to other structurally disordered network-forming materials is also summarised. In all of this work a key theme concerns the rich diversity in the mechanisms of network collapse, which drive the changes in physico-chemical properties of these materials. A more complete picture of the mechanisms is provided by molecular dynamics simulations using theoretical schemes that give a good account of the experimental results.

Density-driven structural transformations in network forming glasses: a high-pressure neutron diffraction study of GeO2 glass up to 17.5 GPa

The structure of GeO(2) glass was investigated at pressures up to 17.5(5) GPa using in situ time-of-flight neutron diffraction with a Paris-Edinburgh press employing sintered diamond anvils. A new methodology and data correction procedure were developed, enabling a reliable measurement of structure factors that are largely free from diamond Bragg peaks. Calibration curves, which are important for neutron diffraction work on disordered materials, were constructed for pressure as a function of applied load for both single and double toroid anvil geometries. The diffraction data are compared to new molecular-dynamics simulations made using transferrable interaction potentials that include dipole-polarization effects. The results, when taken together with those from other experimental methods, are consistent with four densification mechanisms. The first, at pressures up to approximately equal 5 GPa, is associated with a reorganization of GeO(4) units. The second, extending over the range from approximately equal 5 to 10 GPa, corresponds to a regime where GeO(4) units are replaced predominantly by GeO(5) units. In the third, as the pressure increases beyond ~10 GPa, appreciable concentrations of GeO(6) units begin to form and there is a decrease in the rate of change of the intermediate-range order as measured by the pressure dependence of the position of the first sharp diffraction peak. In the fourth, at about 30 GPa, the transformation to a predominantly octahedral glass is achieved and further densification proceeds via compression of the Ge-O bonds. The observed changes in the measured diffraction patterns for GeO(2) occur at similar dimensionless number densities to those found for SiO(2), indicating similar densification mechanisms for both glasses. This implies a regime from about 15 to 24 GPa where SiO(4) units are replaced predominantly by SiO(5) units, and a regime beyond ~24 GPa where appreciable concentrations of SiO(6) units begin to form.

Mechanisms of network collapse in GeO2 glass: high-pressure neutron diffraction with isotope substitution as arbitrator of competing models

The structure of the network forming glass GeO(2) is investigated by making the first application of the method of in situ neutron diffraction with isotope substitution at pressures increasing from ambient to 8 GPa. Of the various models, the experimental results are in quantitative agreement only with molecular dynamics simulations made using interaction potentials that include dipole-polarization effects. When the reduced density ρ/ρ(0) > or approximately equal to 1.16, where ρ(0) is the value at ambient pressure, network collapse proceeds via an interplay between the predominance of distorted square pyramidal GeO(5) units versus octahedral GeO(6) units as they replace tetrahedral GeO(4) units. This replacement necessitates the formation of threefold coordinated oxygen atoms and leads to an increase with density in the number of small rings, where a preference is shown for sixfold rings when ρ/ρ(0) = 1 and fourfold rings when ρ/ρ(0) = 1.64.

Packing and the structural transformations in liquid and amorphous oxides from ambient to extreme conditions

Significance The structures of liquid and amorphous oxides are difficult to solve because of the complexity of their disordered networks, and the adaptability in size of oxide ions to their coordination environments. Particular difficulty is therefore associated with an identification of generic features associated with structural transformations. This paper adopts an empirical approach to find the oxide ion size, and shows that the network structures of a wide variety of disordered oxides can be categorized in terms of the oxygen-packing fraction over an extensive pressure and temperature range. The packing fraction provides a basis for predicting changes in network structures (e.g., from tetrahedral to octahedral) that will affect material properties such as the compressibility and viscosity. Liquid and glassy oxide materials play a vital role in multiple scientific and technological disciplines, but little is known about the part played by oxygen–oxygen interactions in the structural transformations that change their physical properties. Here we show that the coordination number of network-forming structural motifs, which play a key role in defining the topological ordering, can be rationalized in terms of the oxygen-packing fraction over an extensive pressure and temperature range. The result is a structural map for predicting the likely regimes of topological change for a range of oxide materials. This information can be used to forecast when changes may occur to the transport properties and compressibility of, e.g., fluids in planetary interiors, and is a prerequisite for the preparation of new materials following the principles of rational design.

The bound coherent neutron scattering lengths of the oxygen isotopes

The technique of neutron interferometry was used to measure the bound coherent neutron scattering length b(coh) of the oxygen isotopes (17)O and (18)O. From the measured difference in optical path between two water samples, either H(2)(17)O or H(2)(18)O versus H(2)(nat)O, where nat denotes the natural isotopic composition, we obtain b(coh,(17)O) = 5.867(4) fm and b(coh,(18)O) = 6.009(5) fm, based on the accurately known value of b(coh,(nat)O) = 5.805(4) fm which is equal to b(coh,(16)O) within the experimental uncertainty. Our results for b(coh,(17)O) and b(coh,(18)O) differ appreciably from the standard tabulated values of 5.6(5) fm and 5.84(7) fm, respectively. In particular, our measured scattering-length contrast of 0.204(3) fm between (18)O and (nat)O is nearly a factor of 6 greater than the tabulated value, which renders feasible neutron diffraction experiments using (18)O isotope substitution and thereby offers new possibilities for measuring the partial structure factors of oxygen-containing compounds, such as water.

Structure of Glassy Ag–Ge–Se by Neutron Diffraction with Isotope Substitution

Abstract The structure of glassy Ag0.077Ge0.212Se0.711, which lies at y = 0.077 on the Agy(Ge0.23Se0.77)1−y tie-line, was investigated by using the method of neutron diffraction with silver isotope substitution. Two glass transition temperatures were found from a characterisation of the material using modulated differential scanning calorimetry, which indicates a mixed phase material. The diffraction method provides site-specific information on the Ag coordination environment, and gives an average of 3.5(1) Ag–Se nearest-neighbours with a bond distance of 2.65(1) Å together with 0.9(1) Ag–Ag next nearest-neighbours at a distance of 2.9(2) Å. The incorporation of silver does not appear to have a marked effect on the coordination number of Se to other matrix (Ge or Se) atoms, which supports the notion that Ag forms dative bonds with Se lone-pair electrons. A model is given for predicting the change in the Se to matrix atom coordination number when a monovalent metal such as Ag is added to a Se rich Ge–Se base glass.

Topological Ordering and Viscosity in the Glass-Forming Ge–Se System: The Search for a Structural or Dynamical Signature of the Intermediate Phase

The topological ordering of the network structure in vitreous Ge

Optimising the counting times for sample-in-container scattering experiments

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Pressure-dependent structure of the null-scattering alloy Ti0.676Zr0.324

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