Triplet excited electronic state switching induced by hydrogen bonding: A transient absorption spectroscopy and time-dependent DFT study

The solvent plays a decisive role in the photochemistry and photophysics of aromatic ketones. Xanthone (XT) is one such aromatic ketone and its triplet-triplet (T-T) absorption spectra show intriguing solvatochromic behavior. Also, the reactivity of XT towards H-atom abstraction shows an unprecedented decrease in protic solvents relative to aprotic solvents. Therefore, a comprehensive solvatochromic analysis of the triplet-triplet absorption spectra of XT was carried out in conjunction with time dependent density functional theory using the ad hoc explicit solvent model approach. A detailed solvatochromic analysis of the T-T absorption bands of XT suggests that the hydrogen bonding interactions are different in the corresponding triplet excited states. Furthermore, the contributions of non-specific and hydrogen bonding interactions towards differential solvation of the triplet states in protic solvents were found to be of equal magnitude. The frontier molecular orbital and electron density difference analysis of the T-1 and T-2 states of XT indicates that the charge redistribution in these states leads to intermolecular hydrogen bond strengthening and weakening, respectively, relative to the S-0 state. This is further supported by the vertical excitation energy calculations of the XT-methanol supra-molecular complex. The intermolecular hydrogen bonding potential energy curves obtained for this complex in the S-0, T-1, and T-2 states support the model. In summary, we propose that the different hydrogen bonding mechanisms exhibited by the two lowest triplet excited states of XT result in a decreasing role of the n pi* triplet state, and are thus responsible for its reduced reactivity towards H-atom abstraction in protic solvents. (C) 2016 AIP Publishing LLC.

Energy transfer between silicon-oxygen-related defects and Yb3+ in transparent glass ceramics containing Ba2TiSi2O 8 nanocrystals

We report on the conversion of near-ultraviolet radiation of 250-350 nm into near-infrared emission of 970-1100 nm in Yb3+-doped transparent glass ceramics containing Ba2TiSi2O8 nanocrystals due to the energy transfer from the silicon-oxygen-related defects to Yb3+ ions. Efficient Yb3+ emission (F-2(5/2)-> F-2(7/2)) was detected under the excitation of defects absorption at 314 nm. The occurrence of energy transfer is proven by both steady state and time-resolved emission spectra, respectively, at 15 K. The Yb2O3 concentration dependent energy transfer efficiency has also been evaluated, and the maximum value is 65% for 8 mol % Yb2O3 doped glass ceramic. These materials are promising for the enhancement of photovoltaic conversion efficiency of silicon solar cells via spectra modification.

Nanostructured tungsten trioxide photoanodes for solar energy conversion

Nanostructured tungsten trioxide (WO₃) photoelectrodes are potential candidates for the anodic portion of an integrated solar water-splitting device that generates hydrogen fuel and oxygen from water. These nanostructured materials can potentially offer improved performance in photooxidation reactions compared to unstructured materials because of enhancements in light scattering, increases in surface area, and their decoupling of the directions of light absorption and carrier collection. To evaluate the presence of these effects and their contributions toward energy conversion efficiency, a variety of nanostructured WO₃ photoanodes were synthesized by electrodeposition within nanoporous templates and by anodization of tungsten foils. A robust fabrication process was developed for the creation of oriented WO₃ nanorod arrays, which allows for control nanorod diameter and length. Films of nanostructured WO₃ platelets were grown via anodization, the morphology of the films was controlled by the anodization conditions, and the current-voltage performance and spectral response properties of these films were studied. The observed photocurrents were consistent with the apparent morphologies of the nanostructured arrays. Measurements of electrochemically active surface area and other physical characteristics were correlated with observed differences in absorbance, external quantum yield, and photocurrent density for the anodized arrays. The capability to quantify these characteristics and relate them to photoanode performance metrics can allow for selection of appropriate structural parameters when designing photoanodes for solar energy conversion.

I. Application of multi-Regge theory to production processes. II. High energy model for proton-proton scattering

This dissertation consists of two parts. The first part presents an explicit procedure for applying multi-Regge theory to production processes. As an illustrative example, the case of three body final states is developed in detail, both with respect to kinematics and multi-Regge dynamics. Next, the experimental consistency of the multi-Regge hypothesis is tested in a specific high energy reaction; the hypothesis is shown to provide a good qualitative fit to the data. In addition, the results demonstrate a severe suppression of double Pomeranchon exchange, and show the coupling of two "Reggeons" to an external particle to be strongly damped as the particle's mass increases. Finally, with the use of two body Regge parameters, order of magnitude estimates of the multi-Regge cross section for various reactions are given.

The second part presents a diffraction model for high energy proton-proton scattering. This model developed by Chou and Yang assumes high energy elastic scattering results from absorption of the incident wave into the many available inelastic channels, with the absorption proportional to the amount of interpenetrating hadronic matter. The assumption that the hadronic matter distribution is proportional to the charge distribution relates the scattering amplitude for pp scattering to the proton form factor. The Chou-Yang model with the empirical proton form factor as input is then applied to calculate a high energy, fixed momentum transfer limit for the scattering cross section, This limiting cross section exhibits the same "dip" or "break" structure indicated in present experiments, but falls significantly below them in magnitude. Finally, possible spin dependence is introduced through a weak spin-orbit type term which gives rather good agreement with pp polarization data.

Short-pulse laser absorption in very steep plasma density gradients

An analytical fluid model for resonance absorption during the oblique incidence by femtosecond laser pulses on a small-scale-length density plasma [k(0)L is an element of(0.1,10)] is proposed. The physics of resonance absorption is analyzed more clearly as we separate the electric field into an electromagnetic part and an electrostatic part. It is found that the characteristics of the physical quantities (fractional absorption, optimum angle, etc.) in a small-scale-length plasma are quite different from the predictions of classical theory. Absorption processes are generally dependent on the density scale length. For shorter scale length or higher laser intensity, vacuum heating tends to be dominant. It is shown that the electrons being pulled out and then returned to the plasma at the interface layer by the wave field can lead to a phenomenon like wave breaking. This can lead to heating of the plasma at the expanse of the wave energy. It is found that the optimum angle is independent of the laser intensity while the absorption rate increases with the laser intensity, and the absorption rate can reach as high as 25%. (c) 2006 American Institute of Physics.

Short-pulse laser absorption via J x B heating in ultrahigh intensity laser plasma interaction

An analytical fluid model for JxB heating during the normal incidence by a short ultraintense linearly polarized laser on a solid-density plasma is proposed. The steepening of an originally smooth electron density profile as the electrons are pushed inward by the laser is included self-consistently. It is shown that the JxB heating includes two distinct coupling processes depending on the initial laser and plasma conditions: for a moderate intensity (a <= 1), the ponderomotive force of the laser light can drive a large plasma wave at the point n(e)=4 gamma(0)n(c) resonantly. When this plasma wave is damped, the energy is transferred to the plasma. At higher intensity, the electron density is steepened to a high level by the time-independent ponderomotive force, n(e)> 4 gamma(0)n(c), so that no 2 omega resonance will occur, but the longitudinal component of the oscillating ponderomotive field can lead to an absorption mechanism similar to "vacuum heating." (c) 2006 American Institute of Physics.

Experimental and theoretical developments in extended x-ray absorption fine structure (EXAFS) spectroscopy

To obtain accurate information from a structural tool it is necessary to have an understanding of the physical principles which govern the interaction between the probe and the sample under investigation. In this thesis a detailed study of the physical basis for Extended X-ray Absorption Fine Structure (EXAFS) spectroscopy is presented. A single scattering formalism of EXAFS is introduced which allows a rigorous treatment of the central atom potential. A final state interaction formalism of EXAFS is also discussed. Multiple scattering processes are shown to be significant for systems of certain geometries. The standard single scattering EXAFS analysis produces erroneous results if the data contain a large multiple scattering contribution. The effect of thermal vibrations on such multiple scattering paths is also discussed. From symmetry considerations it is shown that only certain normal modes contribute to the Debye-Waller factor for a particular scattering path. Furthermore, changes in the scattering angles induced by thermal vibrations produces additional EXAFS components called modification factors. These factors are shown to be small for most systems.

A study of the physical basis for the determination of structural information from EXAFS data is also presented. An objective method of determining the background absorption and the threshold energy is discussed and involves Gaussian functions. In addition, a scheme to determine the nature of the scattering atom in EXAFS experiments is introduced. This scheme is based on the fact that the phase intercept is a measure of the type of scattering atom. A method to determine bond distances is also discussed and does not require the use of model compounds or calculated phase shifts. The physical basis for this method is the absence of a linear term in the scattering phases. Therefore, it is possible to separate these phases from the linear term containing the distance information in the total phase.

Geometrical effects on the resonance absorption of neutrons

An investigation was conducted to estimate the error when the flat-flux approximation is used to compute the resonance integral for a single absorber element embedded in a neutron source.

The investigation was initiated by assuming a parabolic flux distribution in computing the flux-averaged escape probability which occurs in the collision density equation. Furthermore, also assumed were both wide resonance and narrow resonance expressions for the resonance integral. The fact that this simple model demonstrated a decrease in the resonance integral motivated the more detailed investigation of the thesis.

An integral equation describing the collision density as a function of energy, position and angle is constructed and is subsequently specialized to the case of energy and spatial dependence. This equation is further simplified by expanding the spatial dependence in a series of Legendre polynomials (since a one-dimensional case is considered). In this form, the effects of slowing-down and flux depression may be accounted for to any degree of accuracy desired. The resulting integral equation for the energy dependence is thus solved numerically, considering the slowing down model and the infinite mass model as separate cases.

From the solution obtained by the above method, the error ascribable to the flat-flux approximation is obtained. In addition to this, the error introduced in the resonance integral in assuming no slowing down in the absorber is deduced. Results by Chernick for bismuth rods, and by Corngold for uranium slabs, are compared to the latter case, and these agree to within the approximations made.

Molecular Antennas and Photoactive Nanomaterials based on Energy Transfer Processes

110 p.

Energy transfer and infrared-to-visible upconversion luminescence of Er3+/Yb3+-codoped halide modified tellurite glasses

We report on the energy transfer and frequency upconversion spectroscopic properties of Er3+-doped and Er3+/Yb3+-codoped TeO2-ZnO-Na2O-PbCl2 halide modified tellurite glasses upon excitation with 808 and 978 nm laser diode. Three intense emissions centered at around 529, 546 and 657 nm, alongwith a very weak blue emission at 4 10 nm have clearly been observed for the Er3+/Yb3+-codoped halide modified tellurite glasses upon excitation at 978 nm and the involved mechanisms are explained. The quadratic dependence of fluorescence on excitation laser power confirms the fact that the two-photon contribute to the infrared to green-red upconversion emissions. And the blue upconversion at 410 nm involved a sequential three-photon absorption process. (c) 2005 Elsevier Ltd. All rights reserved.

Effect of microstructure of TiO2 thin films on optical band gap energy

TiO2 coatings are prepared on fused silica with conventional electron beam evaporation deposition. After annealed at different temperatures for four hours, the spectra and XRD patterns of TiO2 thin film are obtained. XRD patterns reveal that only anatase phase can be observed in TiO2 coatings regardless of the different annealing temperatures, and with the increasing annealing temperature, the grain size gradually increases. The relationship between the energy gap and microstructure of anatase is determined and discussed. The quantum confinement effect is observed that with the increasing grain size of TiO2 thin film, the band gap energy shifts from 3.4 eV to 3.21 eV. Moreover, other possible influence of the TiO2 thin-film microstructure, such as surface roughness and thin film absorption, on band gap energy is also expected.

Calculation of the electronic structure of carbon films using electron energy loss spectroscopy.

The detailed understanding of the electronic properties of carbon-based materials requires the determination of their electronic structure and more precisely the calculation of their joint density of states (JDOS) and dielectric constant. Low electron energy loss spectroscopy (EELS) provides a continuous spectrum which represents all the excitations of the electrons within the material with energies ranging between zero and about 100 eV. Therefore, EELS is potentially more powerful than conventional optical spectroscopy which has an intrinsic upper information limit of about 6 eV due to absorption of light from the optical components of the system or the ambient. However, when analysing EELS data, the extraction of the single scattered data needed for Kramers Kronig calculations is subject to the deconvolution of the zero loss peak from the raw data. This procedure is particularly critical when attempting to study the near-bandgap region of materials with a bandgap below 1.5 eV. In this paper, we have calculated the electronic properties of three widely studied carbon materials; namely amorphous carbon (a-C), tetrahedral amorphous carbon (ta-C) and C60 fullerite crystal. The JDOS curve starts from zero for energy values below the bandgap and then starts to rise with a rate depending on whether the material has a direct or an indirect bandgap. Extrapolating a fit to the data immediately above the bandgap in the stronger energy loss region was used to get an accurate value for the bandgap energy and to determine whether the bandgap is direct or indirect in character. Particular problems relating to the extraction of the single scattered data for these materials are also addressed. The ta-C and C60 fullerite materials are found to be direct bandgap-like semiconductors having a bandgaps of 2.63 and 1.59eV, respectively. On the other hand, the electronic structure of a-C was unobtainable because it had such a small bandgap that most of the information is contained in the first 1.2 eV of the spectrum, which is a region removed during the zero loss deconvolution.

Effects of KI encapsulation in single-walled carbon nanotubes by Raman and optical absorption spectroscopy.

The effect of KI encapsulation in narrow (HiPCO) single-walled carbon nanotubes is studied via Raman spectroscopy and optical absorption. The analysis of the data explores the interplay between strain and structural modifications, bond-length changes, charge transfer, and electronic density of states. KI encapsulation appears to be consistent with both charge transfer and strain that shrink both the C-C bonds and the overall nanotube along the axial direction. The charge transfer in larger semiconducting nanotubes is low and comparable with some cases of electrochemical doping, while optical transitions between pairs of singularities of the density of states are quenched for narrow metallic nanotubes. Stronger changes in the density of states occur in some energy ranges and are attributed to polarization van der Waals interactions caused by the ionic encapsulate. Unlike doping with other species, such as atoms and small molecules, encapsulation of inorganic compounds via the molten-phase route provides stable effects due to maximal occupation of the nanotube inner space.

Effect of diets containing various protein and energy levels on some growth parameters, survival and the production of Astacus leptodactylus in different salinities

A factorial experiment was conducted for 60 days to determine of the response of Narrow clawed crayfish Astacus leptodactylus (average weight of 17±2.3 g) to diets containing various protein and energy levels. Nine diets containing three levels of protein (30, 35 and 40 %) and three levels of energy (300,370 and 450 kcal/100g) were formulated and prepared in this trial. Each diet also was used in two levels of salinity include 0 (fresh water) and 12 ppt(Caspian sea water). So this study was conducted with 18 treatments and triplicates random group of 5 crayfish per each 110-litre tank. Weight Gain, Feed conversion ratio (FCR), Protein Efficiency Ratio (PER), Net Protein Utilization (NPU), Daily Food Consumption (DFC), Survival (SVR) and body composition of tail-muscle meat of animal were determined. Comparing the growth parameters in response to interaction between protein, energy and salinity levels demonstrated that all growth parameters have difference between them significantly (p<0.05). Comparing between survival in fresh and Caspian Sea water showed difference significantly. Compare the body composition results indicate the greatest amount of protein absorption in diet number 2(30/370) on fresh water condition. Results from this study indicate that narrow clawed crayfish can be fed a practical diet containing 30% protein and 370 Kcal/100g on non-salinity water which is the optimize CP percentage for their producer’s profits.

Sintered metal foams for acoustic absorption

Metal foams fabricated via sintering offer novel mechanical and acoustic properties. Previously, polymer foams have been used as a means of absorbing acoustic energy. However, the structural applications of these foams are limited. The metal sintering approach offers a cost-effective means for the mass-production of open-cell metal foams. The static flow resistance of sintered metal foams was characterized for a range of practical pore sizes and porosities. The measured values for the flow resistance were subsequently used in a phenomenological acoustic model to predict the impedances and propagation constants of the foams. The predictions were then compared to acoustic measurements. At low frequencies (0-1000Hz), the phenomenological model captures the magnitude and frequency dependence of the absorption. At higher frequencies, as expected, the phenomenological model underpredicted the acoustic properties of the foams. However, an alternative microstructural model demonstrated good correlation to the measured results in this frequency range. The effects of foam type and arrangement on the absorption pattern were examined. General trends were identified for enhancing the low frequency performance of an acoustic absorber incorporating sintered foams.