A comparative study of energy transfer in dye mixtures in monomer and polymer matrices under pulsed laser excitation

This study was conducted to identify the concentration dependence of the operating wavelengths and the relative intensities in which a dye mixture doped polymer optical fibre can operate. A comparative study of the radiative and Forster type energy transfer processes in Coumarin 540:Rhodamine 6G, Coumarin 540:Rhodamine B and Rhodamine 6G:Rhodamine B in methyl methacrylate (MMA) and poly(methyl methacrylate) (PMMA) was done by fabricating a series of dye mixture doped polymer rods which have two emission peaks with varying relative intensities. These rods can be used as preforms for the fabrication of polymer optical fibre amplifiers operating in the multi-wavelength regime. The 445 nm line from an Nd:YAG pumped optical parametric oscillator (OPO) was used as the excitation source for the first two dye pairs and a frequency doubled Nd:YAG laser emitting at 532 nm was used to excite the Rh 6G:Rh B pair. The fluorescence lifetimes of the donor molecule in pure form as well as in the mixtures were experimentally measured in both monomer and polymer matrices by time-correlated single photon counting technique. The energy transfer rate constants and transfer efficiencies were calculated and their dependence on the acceptor concentration was analysed. It was found that radiative energy transfer mechanisms are more efficient in all the three dye pairs in liquid and solid matrices.

Pulsed photoacoustic technique to study nonlinear processes in liquids: Results in toluene

Pulsed photoacoustic measurements have been carried out in toluene at 532 nm wavelength using a Q-switched frequency doubled Nd:YAG laser. The variation of photoacoustic signal amplitude with incident laser power indicates that at lower laser powers one photon absorption takes place at this wavelength while a clear two photon absorption occurs in this liquid at higher laser powers. The studies made here demonstrate that pulsed photoacoustic technique is simple and effective for the investigation of multiphoton processes in liquids.

Observation of two-photon absorption in rhodamine 6G using photoacoustic technique

Two-photon absorption in Rhodamine 6G using the second harmonic of a pulsed Q-switched Nd:YAG laser has been studied by photoacoustic technique. It is observed that there is a competition between one-photon and two-photon absorption processes. At lower concentration the two-photon process is predominant over the one-photon process.

Nd:Glass laser-induced damage to thin films, two-photon excited fluorescence and plasma studies

Laser-induced damage is the principal limiting constraint in the design and operation of high-power laser systems used in fusion and other high-energy laser applications. Therefore, an understanding of the mechanisms which cause the radiation damage to the components employed in building a laser and a knowledge of the damage threshold of these materials are of great importance in designing a laser system and to operate it without appreciable degradation in performance. This thesis, even though covers three distinct problems for investigations using a dye Q-switched multimode Nd:glass laser operating at 1062 nm and emitting 25 ns (FWHM) pulses, lays its main thrust on damage threshold studies on thin films. Using the same glass laser two-photon excited fluorescence in rhodamine 6G and generation and characterisation of a carbon plasma have also been carried out. The thesis is presented in seven chapters.

Nd:Glass Laser-Induced Damage To Thin Films, Two-Photon Excited Fluorescence And Plasma Studies

Laser-induced damage is the principal limiting constraint in the design and operation of high-power laser systems used in fusion and other high-energy laser applications. Therefore, an understanding of the mechanisms which cause the radiation damage to the components employed in building a laser and a knowledge of the damage threshold of these materials are of great importance in designing a laser system and to operate it without appreciable degradation in performance. This thesis, even though covers three distinct problems for investigations using a dye Q-switched multimode Nd:glass laser operating at 1062 nm and emitting 25 ns (FWHM) pulses, lays its main thrust on damage threshold studies on thin films. Using the same glass laser two-photon excited fluorescence in rhodamine 6G and generation and characterisation of a carbon plasma have also been carried out.

Double-autoionization decay of resonantly excited single-electron states

Perturbation theory in the lowest non-vanishing order in interelectron interaction has been applied to the theoretical investigation of double-ionization decays of resonantly excited single-electron states. The formulae for the transition probabilities were derived in the LS coupling scheme, and the orbital angular momentum and spin selection rules were obtained. In addition to the formulae, which are exact in this order, three approximate expressions, which correspond to illustrative model mechanisms of the transition, were derived as limiting cases of the exact ones. Numerical results were obtained for the decay of the resonantly excited Kr 1 3d^{-1}5p[^1P] state which demonstrated quite clearly the important role of the interelectron interaction in double-ionization processes. On the other hand, the results obtained show that low-energy electrons can appear in the photoelectron spectrum below the ionization threshold of the 3d shell. As a function of the photon frequency, the yield of these low-energy electrons is strongly amplified by the resonant transition of the 3d electron to 5p (or to other discrete levels), acting as an intermediate state, when the photon frequency approaches that of the transition.

Three-electron radiative transitions

A new type of many-electron radiative transitions involving three electrons is predicted. The results of their investigation by many-body perturbation theory are presented. New spectral lines observed in the wavelength range of 37.5 to 54.0 nm by means of photon-induced fluorescence spectroscopy (PIFS) following the excitation of the Kr I 3d{^-1}np resonances are reported and compared with the predictions.

Entanglement analysis of atomic processes and quantum registers

During recent years, quantum information processing and the study of N−qubit quantum systems have attracted a lot of interest, both in theory and experiment. Apart from the promise of performing efficient quantum information protocols, such as quantum key distribution, teleportation or quantum computation, however, these investigations also revealed a great deal of difficulties which still need to be resolved in practise. Quantum information protocols rely on the application of unitary and non–unitary quantum operations that act on a given set of quantum mechanical two-state systems (qubits) to form (entangled) states, in which the information is encoded. The overall system of qubits is often referred to as a quantum register. Today the entanglement in a quantum register is known as the key resource for many protocols of quantum computation and quantum information theory. However, despite the successful demonstration of several protocols, such as teleportation or quantum key distribution, there are still many open questions of how entanglement affects the efficiency of quantum algorithms or how it can be protected against noisy environments. To facilitate the simulation of such N−qubit quantum systems and the analysis of their entanglement properties, we have developed the Feynman program. The program package provides all necessary tools in order to define and to deal with quantum registers, quantum gates and quantum operations. Using an interactive and easily extendible design within the framework of the computer algebra system Maple, the Feynman program is a powerful toolbox not only for teaching the basic and more advanced concepts of quantum information but also for studying their physical realization in the future. To this end, the Feynman program implements a selection of algebraic separability criteria for bipartite and multipartite mixed states as well as the most frequently used entanglement measures from the literature. Additionally, the program supports the work with quantum operations and their associated (Jamiolkowski) dual states. Based on the implementation of several popular decoherence models, we provide tools especially for the quantitative analysis of quantum operations. As an application of the developed tools we further present two case studies in which the entanglement of two atomic processes is investigated. In particular, we have studied the change of the electron-ion spin entanglement in atomic photoionization and the photon-photon polarization entanglement in the two-photon decay of hydrogen. The results show that both processes are, in principle, suitable for the creation and control of entanglement. Apart from process-specific parameters like initial atom polarization, it is mainly the process geometry which offers a simple and effective instrument to adjust the final state entanglement. Finally, for the case of the two-photon decay of hydrogenlike systems, we study the difference between nonlocal quantum correlations, as given by the violation of the Bell inequality and the concurrence as a true entanglement measure.

Femtosecond two-photon ionization spectroscopy of the B state of Na_3 clusters

We report time-resolved experiments studying the dynamics of the Na_3 B-X system. Femtosecond pump-probe techniques combined with ion time-of-flight (TOF) and zero kinetic energy (ZEKE) photoelectron spectroscopy allow us to observe the three-dimensional wavepacket motion in the excited Na_3 B state and in the Na_3 X state. The ground state wavepacket is induced by stimulated emission pumping during the pump pulse. The X-state dynamics is dominated by the three vibrational modes of the Na_3. Furthermore we observed pseudorotational wavepacket motion in the B state. We do not observe a fragmentation of the B state within a time interval of 10 ps.

Development of directly modulated high speed telecommunication lasers based on surface defined feedback gratings

High-speed semiconductor lasers are an integral part in the implemen- tation of high-bit-rate optical communications systems. They are com- pact, rugged, reliable, long-lived, and relatively inexpensive sources of coherent light. Due to the very low attenuation window that exists in the silica based optical fiber at 1.55 μm and the zero dispersion point at 1.3 μm, they have become the mainstay of optical fiber com- munication systems. For the fabrication of lasers with gratings such as, distributed bragg reflector or distributed feedback lasers, etching is the most critical step. Etching defines the lateral dimmensions of the structure which determines the performance of optoelectronic devices. In this thesis studies and experiments were carried out about the exist- ing etching processes for InP and a novel dry etching process was de- veloped. The newly developed process was based on Cl2/CH4/H2/Ar chemistry and resulted in very smooth surfaces and vertical side walls. With this process the grating definition was significantly improved as compared to other technological developments in the respective field. A surface defined grating definition approach is used in this thesis work which does not require any re-growth steps and makes the whole fabrication process simpler and cost effective. Moreover, this grating fabrication process is fully compatible with nano-imprint lithography and can be used for high throughput low-cost manufacturing. With usual etching techniques reported before it is not possible to etch very deep because of aspect ratio dependent etching phenomenon where with increasing etch depth the etch rate slows down resulting in non-vertical side walls and footing effects. Although with our de- veloped process quite vertical side walls were achieved but footing was still a problem. To overcome the challenges related to grating defini- tion and deep etching, a completely new three step gas chopping dry etching process was developed. This was the very first time that a time multiplexed etching process for an InP based material system was demonstrated. The developed gas chopping process showed extra ordinary results including high mask selectivity of 15, moderate etch- ing rate, very vertical side walls and a record high aspect ratio of 41. Both the developed etching processes are completely compatible with nano imprint lithography and can be used for low-cost high-throughput fabrication. A large number of broad area laser, ridge waveguide laser, distributed feedback laser, distributed bragg reflector laser and coupled cavity in- jection grating lasers were fabricated using the developed one step etch- ing process. Very extensive characterization was done to optimize all the important design and fabrication parameters. The devices devel- oped have shown excellent performance with a very high side mode suppression ratio of more than 52 dB, an output power of 17 mW per facet, high efficiency of 0.15 W/A, stable operation over temperature and injected currents and a threshold current as low as 30 mA for almost 1 mm long device. A record high modulation bandwidth of 15 GHz with electron-photon resonance and open eye diagrams for 10 Gbps data transmission were also shown.

Effects of different tillage treatments on labile soil organic matter pools and stabilization processes

An improved understanding of soil organic carbon (Corg) dynamics in interaction with the mechanisms of soil structure formation is important in terms of sustainable agriculture and reduction of environmental costs of agricultural ecosystems. However, information on physical and chemical processes influencing formation and stabilization of water stable aggregates in association with Corg sequestration is scarce. Long term soil experiments are important in evaluating open questions about management induced effects on soil Corg dynamics in interaction with soil structure formation. The objectives of the present thesis were: (i) to determine the long term impacts of different tillage treatments on the interaction between macro aggregation (>250 µm) and light fraction (LF) distribution and on C sequestration in plots differing in soil texture and climatic conditions. (ii) to determine the impact of different tillage treatments on temporal changes in the size distribution of water stable aggregates and on macro aggregate turnover. (iii) to evaluate the macro aggregate rebuilding in soils with varying initial Corg contents, organic matter (OM) amendments and clay contents in a short term incubation experiment. Soil samples were taken in 0-5 cm, 5-25 cm and 25-40 cm depth from up to four commercially used fields located in arable loess regions of eastern and southern Germany after 18-25 years of different tillage treatments with almost identical experimental setups per site. At each site, one large field with spatially homogenous soil properties was divided into three plots. One of the following three tillage treatments was carried in each plot: (i) Conventional tillage (CT) with annual mouldboard ploughing to 25-30 cm (ii) mulch tillage (MT) with a cultivator or disc harrow 10-15 cm deep, and (iii) no tillage (NT) with direct drilling. The crop rotation at each site consisted of sugar beet (Beta vulgaris L.) - winter wheat (Triticum aestivum L.) - winter wheat. Crop residues were left on the field and crop management was carried out following the regional standards of agricultural practice. To investigate the above mentioned research objectives, three experiments were conducted: Experiment (i) was performed with soils sampled from four sites in April 2010 (wheat stand). Experiment (ii) was conducted with soils sampled from three sites in April 2010, September 2011 (after harvest or sugar beet stand), November 2011 (after tillage) and April 2012 (bare soil or wheat stand). An incubation study (experiment (iii)) was performed with soil sampled from one site in April 2010. Based on the aforementioned research objectives and experiments the main findings were: (i) Consistent results were found between the four long term tillage fields, varying in texture and climatic conditions. Correlation analysis of the yields of macro aggregate against the yields of free LF ( ≤1.8 g cm-3) and occluded LF, respectively, suggested that the effective litter translocation in higher soil depths and higher litter input under CT and MT compensated in the long term the higher physical impact by tillage equipment than under NT. The Corg stocks (kg Corg m−2) in 522 kg soil, based on the equivalent soil mass approach (CT: 0–40 cm, MT: 0–38 cm, NT: 0–36 cm) increased in the order CT (5.2) = NT (5.2) < MT (5.7). Significantly (p ≤ 0.05) highest Corg stocks under MT were probably a result of high crop yields in combination with reduced physical tillage impact and effective litter incorporation, resulting in a Corg sequestration rate of 31 g C-2 m-2 yr-1. (ii) Significantly higher yields of macro aggregates (g kg-2 soil) under NT (732-777) and MT (680-726) than under CT (542-631) were generally restricted to the 0-5 cm sampling depth for all sampling dates. Temporal changes on aggregate size distribution were only small and no tillage induced net effect was detectable. Thus, we assume that the physical impact by tillage equipment was only small or the impact was compensated by a higher soil mixing and effective litter translocation into higher soil depths under CT, which probably resulted in a high re aggregation. (iii) The short term incubation study showed that macro aggregate yields (g kg-2 soil) were higher after 28 days in soils receiving OM (121.4-363.0) than in the control soils (22.0-52.0), accompanied by higher contents of microbial biomass carbon and ergosterol. Highest soil respiration rates after OM amendments within the first three days of incubation indicated that macro aggregate formation is a fast process. Most of the rebuilt macro aggregates were formed within the first seven days of incubation (42-75%). Nevertheless, it was ongoing throughout the entire 28 days of incubation, which was indicated by higher soil respiration rates at the end of the incubation period in OM amended soils than in the control soils. At the same time, decreasing carbon contents within macro aggregates over time indicated that newly occluded OM within the rebuilt macro aggregates served as Corg source for microbial biomass. The different clay contents played only minor role in macro aggregate formation under the particular conditions of the incubation study. Overall, no net changes on macro aggregation were identified in the short term. Furthermore, no indications for an effective Corg sequestration on the long term under NT in comparison to CT were found. The interaction of soil disturbance, litter distribution and the fast re aggregation suggested that a distinct steady state per tillage treatment in terms of soil aggregation was established. However, continuous application of MT with a combination of reduced physical tillage impact and effective litter incorporation may offer some potential in improving the soil structure and may therefore prevent incorporated LF from rapid decomposition and result in a higher C sequestration on the long term.

Effects of transformation processes in 'jubraka' agroforestry systems of the Nuba Mountains, Sudan, on nutrient fluxes

Intensification processes in homegardens of the Nuba Mountains, Sudan, raise concerns about strongly positive carbon (C) and nutrient balances which are expected to lead to substantial element losses from these agroecosystems, in particular via soil gaseous emissions. Therefore, this thesis aimed at the quantification of C, nitrogen (N), phosphorus (P) and potassium (K) input and output fluxes with a special focus on soil gaseous losses, and the calculation of respective element balances. A further focus in this thesis was rainfall, a valuable resource for rain-fed agriculture in the Nuba Mountains. To minimize negative consequences of the high variability of rainfall, risk reducing mechanisms were developed by rain-fed farmers that may lose their efficacy in the course of climate change effects predicted for East Africa. Therefore, the second objective of this study was to examine possible changes in rainfall amounts during the last 60 years and to provide reliable risk and probability statements of rainfall-induced events of agricultural importance to rain-fed farmers in the Nuba Mountains. Soil gaseous emissions of C (in form of CO2) and N (in form of NH3 and N2O) of two traditional and two intensified homegardens were determined with a portable dynamic closed chamber system. For C gaseous emission rates reached their peak at the onset of the rainy season (2,325 g CO2-C ha-1 h-1 in an intensified garden type) and for N during the rainy season (16 g NH3-N ha-1 h-1 and 11.3 g N2O-N ha-1 h-1, in a traditional garden type). Data indicated cumulative annual emissions of 5,893 kg CO2-C ha-1, 37 kg NH3-N ha-1, and 16 kg N2O-N ha-1. For the assessment of the long-term productivity of the two types of homegardens and the identification of pathways of substantial element losses, a C and nutrient budget approach was used. In three traditional and three intensified homegardens observation plots were selected. The following variables were quantified on each plot between June and December in 2010: soil amendments, irrigation, biomass removal, symbiotic N2 fixation, C fixation by photosynthesis, atmospheric wet and dry deposition, leaching and soil gaseous emissions. Annual balances for C and nutrients amounted to -21 kg C ha-1, -70 kg N ha-1, 9 kg P ha-1 and -117 kg K ha-1 in intensified homegardens and to -1,722 kg C ha-1, -167 kg N ha-1, -9 kg P ha-1 and -74 kg K ha-1 in traditional homegardens. For the analysis of rainfall data, the INSTAT+ software allowed to aggregate long-term daily rainfall records from the Kadugli and Rashad weather stations into daily, monthly and annual intervals and to calculate rainfall-induced events of agricultural importance. Subsequently, these calculated values and events were checked for possible monotonic trends by Mann-Kendall tests. Over the period from 1970 to 2009, annual rainfall did not change significantly for either station. However, during this period an increase of low rainfall events coinciding with a decline in the number of medium daily rainfall events was observed in Rashad. Furthermore, the availability of daily rainfall data enabled frequency and conditional probability calculations that showed either no statistically significant changes or trends resulting only in minor changes of probabilities.

Convex linear combination processes for compositions

Aitchison and Bacon-Shone (1999) considered convex linear combinations of compositions. In other words, they investigated compositions of compositions, where the mixing composition follows a logistic Normal distribution (or a perturbation process) and the compositions being mixed follow a logistic Normal distribution. In this paper, I investigate the extension to situations where the mixing composition varies with a number of dimensions. Examples would be where the mixing proportions vary with time or distance or a combination of the two. Practical situations include a river where the mixing proportions vary along the river, or across a lake and possibly with a time trend. This is illustrated with a dataset similar to that used in the Aitchison and Bacon-Shone paper, which looked at how pollution in a loch depended on the pollution in the three rivers that feed the loch. Here, I explicitly model the variation in the linear combination across the loch, assuming that the mean of the logistic Normal distribution depends on the river flows and relative distance from the source origins

Processes influencing ozone levels in Alaskan forest fire plumes during long-range transport over the North Atlantic

A case of long-range transport of a biomass burning plume from Alaska to Europe is analyzed using a Lagrangian approach. This plume was sampled several times in the free troposphere over North America, the North Atlantic and Europe by three different aircraft during the IGAC Lagrangian 2K4 experiment which was part of the ICARTT/ITOP measurement intensive in summer 2004. Measurements in the plume showed enhanced values of CO, VOCs and NOy, mainly in form of PAN. Observed O3 levels increased by 17 ppbv over 5 days. A photochemical trajectory model, CiTTyCAT, was used to examine processes responsible for the chemical evolution of the plume. The model was initialized with upwind data and compared with downwind measurements. The influence of high aerosol loading on photolysis rates in the plume was investigated using in situ aerosol measurements in the plume and lidar retrievals of optical depth as input into a photolysis code (Fast-J), run in the model. Significant impacts on photochemistry are found with a decrease of 18% in O3 production and 24% in O3 destruction over 5 days when including aerosols. The plume is found to be chemically active with large O3 increases attributed primarily to PAN decomposition during descent of the plume toward Europe. The predicted O3 changes are very dependent on temperature changes during transport and also on water vapor levels in the lower troposphere which can lead to O3 destruction. Simulation of mixing/dilution was necessary to reproduce observed pollutant levels in the plume. Mixing was simulated using background concentrations from measurements in air masses in close proximity to the plume, and mixing timescales (averaging 6.25 days) were derived from CO changes. Observed and simulated O3/CO correlations in the plume were also compared in order to evaluate the photochemistry in the model. Observed slopes change from negative to positive over 5 days. This change, which can be attributed largely to photochemistry, is well reproduced by multiple model runs even if slope values are slightly underestimated suggesting a small underestimation in modeled photochemical O3 production. The possible impact of this biomass burning plume on O3 levels in the European boundary layer was also examined by running the model for a further 5 days and comparing with data collected at surface sites, such as Jungfraujoch, which showed small O3 increases and elevated CO levels. The model predicts significant changes in O3 over the entire 10 day period due to photochemistry but the signal is largely lost because of the effects of dilution. However, measurements in several other BB plumes over Europe show that O3 impact of Alaskan fires can be potentially significant over Europe.

Data assimilation: From photon counts to Earth System forecasts

Data assimilation – the set of techniques whereby information from observing systems and models is combined optimally – is rapidly becoming prominent in endeavours to exploit Earth Observation for Earth sciences, including climate prediction. This paper explains the broad principles of data assimilation, outlining different approaches (optimal interpolation, three-dimensional and four-dimensional variational methods, the Kalman Filter), together with the approximations that are often necessary to make them practicable. After pointing out a variety of benefits of data assimilation, the paper then outlines some practical applications of the exploitation of Earth Observation by data assimilation in the areas of operational oceanography, chemical weather forecasting and carbon cycle modelling. Finally, some challenges for the future are noted.