Development and Application of Embedding Methods for the Simulation of Large Chemical Systems

The high computational cost of correlated wavefunction theory (WFT) calculations has motivated the development of numerous methods to partition the description of large chemical systems into smaller subsystem calculations. For example, WFT-in-DFT embedding methods facilitate the partitioning of a system into two subsystems: a subsystem A that is treated using an accurate WFT method, and a subsystem B that is treated using a more efficient Kohn-Sham density functional theory (KS-DFT) method. Representation of the interactions between subsystems is non-trivial, and often requires the use of approximate kinetic energy functionals or computationally challenging optimized effective potential calculations; however, it has recently been shown that these challenges can be eliminated through the use of a projection operator. This dissertation describes the development and application of embedding methods that enable accurate and efficient calculation of the properties of large chemical systems.

Chapter 1 introduces a method for efficiently performing projection-based WFT-in-DFT embedding calculations on large systems. This is accomplished by using a truncated basis set representation of the subsystem A wavefunction. We show that naive truncation of the basis set associated with subsystem A can lead to large numerical artifacts, and present an approach for systematically controlling these artifacts.

Chapter 2 describes the application of the projection-based embedding method to investigate the oxidative stability of lithium-ion batteries. We study the oxidation potentials of mixtures of ethylene carbonate (EC) and dimethyl carbonate (DMC) by using the projection-based embedding method to calculate the vertical ionization energy (IE) of individual molecules at the CCSD(T) level of theory, while explicitly accounting for the solvent using DFT. Interestingly, we reveal that large contributions to the solvation properties of DMC originate from quadrupolar interactions, resulting in a much larger solvent reorganization energy than that predicted using simple dielectric continuum models. Demonstration that the solvation properties of EC and DMC are governed by fundamentally different intermolecular interactions provides insight into key aspects of lithium-ion batteries, with relevance to electrolyte decomposition processes, solid-electrolyte interphase formation, and the local solvation environment of lithium cations.

Monitoring the trophic status of reservoirs

The current situation of regional, rather' than national, problems of eutrophication in standing waters has been widely aired in recent reports. A reliable, quantitative data base is a prerequisite to future trend monitoring, a concensus view of those reports. The objective of this report is to establish requirements, methodology and a minimal data set for nutrient and algae status in water supply reservoirs in England which may be used as a protocol for future trend monitoring.A pilot study has been carried out to assess the relative merits of different sampling strategies, the choice of which has major implications for the cost of sample collection. This short report suggests that consider the possibility of designating a few sites as ”baseline sites” at which detailed changes in trophic status as monitored by the more labour-intensive parameters would be collected on a regular, long term basis to help in the interpretation of the low cost survey results.

Advancements in jet turbulence and noise modeling: accurate one-way solutions and empirical evaluation of the nonlinear forcing of wavepackets

Jet noise reduction is an important goal within both commercial and military aviation. Although large-scale numerical simulations are now able to simultaneously compute turbulent jets and their radiated sound, lost-cost, physically-motivated models are needed to guide noise-reduction efforts. A particularly promising modeling approach centers around certain large-scale coherent structures, called wavepackets, that are observed in jets and their radiated sound. The typical approach to modeling wavepackets is to approximate them as linear modal solutions of the Euler or Navier-Stokes equations linearized about the long-time mean of the turbulent flow field. The near-field wavepackets obtained from these models show compelling agreement with those educed from experimental and simulation data for both subsonic and supersonic jets, but the acoustic radiation is severely under-predicted in the subsonic case. This thesis contributes to two aspects of these models. First, two new solution methods are developed that can be used to efficiently compute wavepackets and their acoustic radiation, reducing the computational cost of the model by more than an order of magnitude. The new techniques are spatial integration methods and constitute a well-posed, convergent alternative to the frequently used parabolized stability equations. Using concepts related to well-posed boundary conditions, the methods are formulated for general hyperbolic equations and thus have potential applications in many fields of physics and engineering. Second, the nonlinear and stochastic forcing of wavepackets is investigated with the goal of identifying and characterizing the missing dynamics responsible for the under-prediction of acoustic radiation by linear wavepacket models for subsonic jets. Specifically, we use ensembles of large-eddy-simulation flow and force data along with two data decomposition techniques to educe the actual nonlinear forcing experienced by wavepackets in a Mach 0.9 turbulent jet. Modes with high energy are extracted using proper orthogonal decomposition, while high gain modes are identified using a novel technique called empirical resolvent-mode decomposition. In contrast to the flow and acoustic fields, the forcing field is characterized by a lack of energetic coherent structures. Furthermore, the structures that do exist are largely uncorrelated with the acoustic field. Instead, the forces that most efficiently excite an acoustic response appear to take the form of random turbulent fluctuations, implying that direct feedback from nonlinear interactions amongst wavepackets is not an essential noise source mechanism. This suggests that the essential ingredients of sound generation in high Reynolds number jets are contained within the linearized Navier-Stokes operator rather than in the nonlinear forcing terms, a conclusion that has important implications for jet noise modeling.

Comparison of cerium-doped Lu2Si2O7 and Lu2SiO5 scintillators

In this paper, high optical quality cerium-doped lutetium pyrosilicate(LPS:Ce) crystal has been grown by Czochralski method with the seed oriented along cleavage plane (1 1 0). The structure, segregation coefficient of Ce3+ and optical characterization of LPS:Ce crystal have been compared with those of LSO:Ce crystal. The results show that LPS:Ce has the advantage over LSO:Ce by having a larger segregation coefficient of Ce3+, lower cost of starting material, lower melting point and only one luminescence mechanism. Thus, LPS:Ce crystal offers an attractive alternative to LSO:Ce for scintillator applications. (c) 2005 Elsevier B.V. All rights reserved.

An investigation of the recaptures rates for tagged brown trout stocked into the River Ribble

The angling season for non-migratory brown trout, in the Environment Agency (EA) North West Region, runs from March 15th to September 30th. Each year, large numbers of farm reared brown trout are stocked into the rivers of the North West Region's Central Area. In 1994, approximately 20,000 brown trout were introduced into the River systems of the Lune, Wyre and Ribble by local angling clubs and fishery owners. Most of these fish were stocked at a length greater than that defined by local byelaws as the takeable size (200mm). Introductions are made to supplement the existing wild brown trout populations within the river and increase the probability of an angler catching a fish. Stocking with fish of a sufficient length allows the successful angler to remove the catch for their own use. In this way, stretches of the rivers are effectively managed as "put and take" fisheries for brown trout. A number of brown trout fingerlings are also introduced each year by angling clubs and fishery owners. These are stocked with the expectation that the fish will survive in the river to grow, over-winter, and eventually attain a takable size with an increased degree of "wildness". The lower cost of fingerlings, as opposed to trout of a takable length, makes their introduction more attractive to angling clubs since a greater number can be stocked for a given cost. Although the practise of stocking brown trout has occurred for many years in the Central Area, there is little information of its success in terms of increasing anglers catches, or the survival offish introduced. This study was initiated to determine the recapture rates by angling of brown trout following their introduction into a river fishery. The information gained from this study can then be used to give guidance to angling clubs and fishery owners on the optimal strategies for stocking fish.

The Many Lovers of Jane Austen: Irony & Parody

Master in Literature and Literary Science

Effects of photoperiod on growth of larvae and juveniles of the anemonefish Amphiprion melanopus

Rearing of anemonefishes is now relatively routine compared to the culture of cardinalfishes (Apogonidae) or angelfishes (Pomacanthidae). However, it is still a labor intensive, time intensive and expensive procedure. To reduce time and cost of rearing anemonefishes, experiments were undertaken to improve the methods for rearing Amphiprion melanopus. These experiments were conducted to determine the effect of the length of photoperiod on larval duration, growth to metamorphosis and early juvenile phase. Growth of larvae was significantly faster and the duration of the larval phase was significantly shorter, under a photoperiod of 16 hours light/8 hours dark, compared to the photoperiods of 12 hours light/12 hours dark and 24 hours light/0 hours dark.

Effects of Spring Temperatures on the Strength of Selection on Timing of Reproduction in a Long-Distance Migratory Bird

Climate change has differentially affected the timing of seasonal events for interacting trophic levels, and this has often led to increased selection on seasonal timing. Yet, the environmental variables driving this selection have rarely been identified, limiting our ability to predict future ecological impacts of climate change. Using a dataset spanning 31 years from a natural population of pied flycatchers (Ficedula hypoleuca), we show that directional selection on timing of reproduction intensified in the first two decades (1980-2000) but weakened during the last decade (2001-2010). Against expectation, this pattern could not be explained by the temporal variation in the phenological mismatch with food abundance. We therefore explored an alternative hypothesis that selection on timing was affected by conditions individuals experience when arriving in spring at the breeding grounds: arriving early in cold conditions may reduce survival. First, we show that in female recruits, spring arrival date in the first breeding year correlates positively with hatch date; hence, early-hatched individuals experience colder conditions at arrival than late-hatched individuals. Second, we show that when temperatures at arrival in the recruitment year were high, early-hatched young had a higher recruitment probability than when temperatures were low. We interpret this as a potential cost of arriving early in colder years, and climate warming may have reduced this cost. We thus show that higher temperatures in the arrival year of recruits were associated with stronger selection for early reproduction in the years these birds were born. As arrival temperatures in the beginning of the study increased, but recently declined again, directional selection on timing of reproduction showed a nonlinear change. We demonstrate that environmental conditions with a lag of up to two years can alter selection on phenological traits in natural populations, something that has important implications for our understanding of how climate can alter patterns of selection in natural populations.

Markets, marketing and production issues for aquaculture in East Africa: the case of Uganda

Aquaculture is currently responsible for an insignificant proportion of total fish production in Uganda. However, given the increasing demand for fresh fish in urban and peri-urban araes, and threats to the supply of fish from natural catch fisheries, the potential exists for a strong market in aquaculture. Small-scale fish farmers located relatively close to markets or all-season roads, and who can supply consistent and high quality produce, will have the widest range of marketing opportunities, and will likely be within the area of operation of potential traders and intermediaries that deliver fish to markets. Fish farmers that are not close to roads, or produce unreliable quantities and variable quality products may face high transaction costs of marketing their product, and decreasing net returns to production. The authors found that significant on-farm labor, and access to input markets are important factors leading to positive net returns to fish production. Areas with high population density and relatively low wages will be well suited to labor intensive aquaculture. The authors concluded that aquaculture development has good potential in certain areas of Uganda and should therefore be pursued as a potential development pathway. However, policy makers should consider the importance of the price of fresh fish relative to the cost of labor, as well as other factors including the importance of smallholder credit and access to extension services, when directing investments in aquaculture technology.

Comparative study of hatching rates of African catfish (Clarias gariepinus Burchell 1822) eggs on different substrates

The hatching rates of African catfish (Clarias gariepinus) eggs on four natural substrates: the roots of Nile cabbage (Pistia stratiotes), water hyacinth (Eichhornia crassipes), pond weed (Ceratophyllum dermasum) and green grass leaves (Commelina sp.), and four artificial substrates: sisal mats, nylon mats, papyrus mats and kakaban mats, was assessed. Concrete slabs were used as control. The natural substrates performed better than the artificial ones. Pistia roots gave the best mean hatching rate of 66.2 ± 3.62%. Green grass leaves were second with a mean rate of 54.0 ± 3.46%, water hyacinth was third with 49.7 ± 3.16% and Ceratophyllum fourth with a mean of 13.0 ± 2.37%. Concrete slabs gave a mean rate of 18.6 ± 2.8%, sisal mats 18.6 ± 2.0%, papyrus 12.2 ± 1.2% and kakaban 11.8 ± 1.9%. Nylon mats were the last, with a mean rate of 4.0 ± 0.7%. The best performing natural substrates were those with the ability to float and thin fibrous roots that seemed to allow higher aeration of the eggs during incubation. The cost of using natural substrates was minimal.

Technical efficiency in artisanal fisheries (AF) in Badagry local government area of Lagos State, Nigeria

This study examined the technical efficiency in artisanal fisheries in Lagos State of Nigeria. The study employed a two stage random sampling procedure for the selection of 120 respondents. The analytical techniques involved descriptive statistics and estimation of technical efficiency following maximum likelihood estimation (MLE) procedure available in FRONTIER 4.1. The MLE result of the stochastic frontier production function showed that hired labour, cost of repair and capital items are critical factors that influences productivity of artisanal fishermen with the coefficient of hired labour being highly elastic. This implies that employing more labour will significantly increase the catch in the study area. The predicted farm efficiency with an average value of 0.92 showed that there is a marginal potential of about 8 percent to increase the catch, hence the income of the fishermen. The study further examined the factors that influence productivity of fishermen in the study area. Year of education, mode of operation and frequency of fishing have important implication on the technical efficiency of fishermen in the study area.

Genetic improvement of freshwater prawn, Macrobrachium rosenbergii (de Man) in India. Phase two: annual report for period January to December 2012

Macrobrachiurn rosenbergii is one of the widely cultured freshwater prawn species globally. India was the third largest producer of this species in 2007 and its aquaculture production rose to 43,000 metric tons (t) in 2005 froin less than 500 t in 1995. However, since then production has been declining and in 2008-09 it was 12,856 t, a reduction of more than 70% compared to 2005. There are several contributing factors to this decline, such as slow growth rate, poor survival, disease outbreaks, increase in cost of production, and availability of low risk alternative fish species. However, there is a consensus that poor seed quality leading to unsatisfactory growth and survival rates in ponds is one of the major reasons. Hence, the development of a systematic selective breeding program aimed at improving growth rate and ensuring high survival rate of this species was deemed a high priority. The Central Institute of Freshwater Aquaculture (CIFA), Bhubaneswar, India in collaboration with the WorldFish Center, Malaysia initiated a selective breeding program for this species in 2007.

Analytical approximations for the modal acoustic impedances of simply supported, rectangular plates.

Coupling of the in vacuo modes of a fluid-loaded, vibrating structure by the resulting acoustic field, while known to be negligible for sufficiently light fluids, is still only partially understood. A particularly useful structural geometry for the study of this problem is the simply supported, rectangular flat plate, since it exhibits all the relevant physical features while still admitting an analytical description of the modes. Here the influence of the fluid can be expressed in terms of a set of doubly infinite integrals over wave number: the modal acoustic impedances. Closed-form solutions for these impedances do not exist and, while their numerical evaluation is possible, it greatly increases the computational cost of solving the coupled system of modal equations. There is thus a need for accurate analytical approximations. In this work, such approximations are sought in the limit where the modal wavelength is small in comparison with the acoustic wavelength and the plate dimensions. It is shown that contour integration techniques can be used to derive analytical formulas for this regime and that these formulas agree closely with the results of numerical evaluations. Previous approximations [Davies, J. Sound Vib. 15(1), 107-126 (1971)] are assessed in the light of the new results and are shown to give a satisfactory description of real impedance components, but (in general) erroneous expressions for imaginary parts.

Ecological and economic consequences of hypoxia: Topic 2 Report for the Integrated Assessment on Hypoxia in the Gulf of Mexico

In this report we have attempted to evaluate the ecological and economic consequences of hypoxia in the northern Gulf of Mexico. Although our initial approach was to rely on published accounts, we quickly realized that the body of published literature deahng with hypoxia was limited, and we would have to conduct our own exploratory analysis of existing Gulf data, or rely on published accounts from other systems to infer possible or potential effects of hypoxia. For the economic analysis, we developed a conceptual model of how hypoxia-related impacts could affect fisheries. Our model included both supply and demand components. The supply model had two components: (1) a physical production function for fish or shrimp, and (2) the cost of fishing. If hypoxia causes the cost of a unit of fishing effort to change, then this will result in a shift in supply. The demand model considered how hypoxia might affect the quality of landed fish or shrimp. In particular, the market value per pound is lower for small shrimp than for large shrimp. Given the limitations of the ecological assessment, the shallow continental shelf area affected by hypoxia does show signs of hypoxia-related stress. While current ecological conditions are a response to a variety of stressors, the effects of hypoxia are most obvious in the benthos that experience mortality, elimination of larger long-lived species, and a shifting of productivity to nonhypoxic periods (energy pulsing). What is not known is whether hypoxia leads to higher productivity during productive periods, or simply to a reduction of productivity during oxygen-stressed periods. The economic assessment based on fisheries data, however, failed to detect effects attributable to hypoxia. Overall, fisheries landings statistics for at least the last few decades have been relatively constant. The failure to identify clear hypoxic effects in the fisheries statistics does not necessarily mean that they are absent. There are several possibilities: (1) hypoxic effects are small relative to the overall variability in the data sets evaluated; (2) the data and the power of the analyses are not adequate; and (3) currently there are no hypoxic effects on fisheries. Lack of identified hypoxic effects in available fisheries data does not imply that effects would not occur should conditions worsen. Experience with other hypoxic zones around the globe shows that both ecological and fisheries effects become progressively more severe as hypoxia increases. Several large systems around the globe have suffered serious ecological and economic consequences from seasonal summertime hypoxia; most notable are the Kattegat and Black Sea. The consequences range from localized loss of catch and recruitment failure to complete system-wide loss of fishery species. If experiences in other systems are applicable to the Gulf of Mexico, then in the face of worsening hypoxic conditions, at some point fisheries and other species will decline, perhaps precipitously.

Lobster trap debris in the Florida Keys National Marine Sanctuary: distribution, abundance, density, and patterns of accumulation

The fishery for spiny lobster Panulirus argus in the Florida Keys National Marine Sanctuary is well chronicled, but little information is available on the prevalence of lost or abandoned lobster traps. In 2007, towed-diver surveys were used to identify and count pieces of trap debris and any other marine debris encountered. Trap debris density (debris incidences/ha) in historic trap-use zones and in representative benthic habitats was estimated. Trap debris was not proportionally distributed with fishing effort. Coral habitats had the greatest density of trap debris despite trap fishers’ reported avoidance of coral reefs while fishing. The accumulation of trap debris on coral emphasizes the role of wind in redistributing traps and trap debris in the sanctuary. We estimated that 85,548 ± 23,387 (mean ± SD) ghost traps and 1,056,127 ± 124,919 nonfishing traps or remnants of traps were present in the study area. Given the large numbers of traps in the fishery and the lack of effective measures for managing and controlling the loss of gear, the generation of trap debris will likely continue in proportion to the number of traps deployed in the fishery. Focused removal of submerged trap debris from especially vulnerable habitats such as reefs and hardbottom, where trap debris density is high, would mitigate key habitat issues but would not address ghost fishing or the cost of lost gear.