Structural and spectroscopic properties of the diazocarbene radical (CNN) and its ions CNN(+) and CNN(-): a high-level theoretical investigation

The diazocarbene radical, CNN, and the ions CNN(+) and CNN(-) were investigated at a high level of theory. Very accurate structural parameters for the states X(3)Sigma(-) and A(3)Pi of CNN, and X(2)Pi of both CNN(+) and CNN(-) were obtained with the UCCSD(T) method using correlated-consistent basis functions with extrapolations to the complete basis set limit, with valence only and also with all electrons correlated. Harmonic and anharmonic frequencies were obtained for all species and the Renner parameter and average frequencies evaluated for the Pi states. At the UCCSD(T)/CBS(T-5) level of theory, Delta(f)H(0 K) = 138.89 kcal/mol and Delta(f)H(298 K) = 139.65 kcal/mol were obtained for diazocarbene; for the ionization potential and the electron affinity of CNN, 10.969 eV (252.95 kcal/mol), and 1.743 eV (40.19 kcal/mol), respectively, are predicted. Geometry optimization was also carried out with the CASSCF/MRCI/CBS(T-5) approach for the states X(3)Sigma(-) A(3)Pi, and a(1)Delta of CNN, and with the CASSCF/MRSDCI/aug-cc-pVTZ approach for the states b(1)Sigma(+), c(1)Pi, d(1)Sigma(-), and B(3)Sigma(-), and excitation energies (T(e)) evaluated. Vertical energies were calculated for 15 electronic states, thus improving on the accuracy of the five transitions already described, and allowing for a reliable overview of a manifold of other states, which is expected to guide future spectroscopic experiments. This study corroborates the experimental assignment for the vertical transition X (3)Sigma(-) <- E (3)Pi.

New Molecular Species of Potential Interest to Atmospheric Chemistry: Isomers on the [H, S(2), Br] Potential Energy Surface

This work reports a state-of-the-art theoretical characterization of four new sulfur-bromine species and five transition states on the [H, S(2), Br] potential energy surface. Our highest level theoretical approach employed the method coupled cluster singles and doubles with perturbative contributions of connected triples, CCSD(T), along with the series of correlation-consistent basis sets and with extrapolation to the complete basis set (CBS) limit in the optimization of the geometrical parameters and to quantify the energetic quantities. The structural and vibrational frequencies here reported are unique and represent the most accurate investigation to date of these species. The global minimum corresponds to a skewed structure HSSBr with a disulfide bond; this is followed by a pyramidal-like structure, SSHBr, 18.85 kcal/mol above the minimum. Much higher in energy, we found another skewed structure, HSBrS (50.29 kcal/mol), with one S-Br dative-type bond, and another pyramidal-like one, HBrSS (109.80 kcal/mol), with two S-Br dative-type bonds. The interconversion of HSSBr into SSHBr can occur via a transfer of either the hydrogen or the bromine atom but involves a very high barrier of about 43 kcal/mol. These molecules are potentially a new route of coupling the sulfur and bromine chemistry in the atmosphere, and conditions of high concentration of H(2)S like in volcanic eruptions might contribute to their formation. We note that HSSBr can act as a reservoir molecule for the reaction between the radicals HSS and Br. Also, an assessment of the methods DFT/B3LYP/CBS and MP2/CBS relative to CCSD(T)/CBS provides insights on the expected performance of these methods on the characterization of polysulfides and also of more complex systems containing disulfide bridges.

Optimization of performances of gelatin/LiBF(4)-based polymer electrolytes by plasticizing effects

Gelatin is a cheap and abundant natural product with very good biodegradation properties and can be used to obtain acetic acid or LiClO(4)-based gel polymer electrolytes (GPEs) with high ionic conductivity and good stability. This article presents results of GPEs obtained by the plasticization of gelatin and addition of LiBF(4), where the optimization of the system was achieved by using a factorial design type 22 with two variables: glycerol and LiBF(4). From this analysis it was stated that the effect of glycerol as a plasticizer on the ionic conductivity results is much more important than the effect obtained by varying the lithium salt content or the effect of the interaction of both variables. Also all the samples were characterized by X-ray diffraction measurements, UV-vis-NIR spectroscopy and scanning electron microscopy (SEM) and impedance spectroscopy. The ionic conductivity results of all analyzed samples as a function of temperature obey predominantly an Arrhenius relationship and the samples are stable up to 160 degrees C. Good conductivity results combined with transparency and good adhesion to the electrodes have shown that gelatin-based GPEs are very promising materials to be used as solid electrolytes in electrochromic devices. (C) 2009 Elsevier Ltd. All rights reserved.

Task assignment optimization in SAP Extended WarehouseManagement

Nowadays in the world of mass consumption there is big demand for distributioncenters of bigger size. Managing such a center is a very complex and difficult taskregarding to the different processes and factors in a usual warehouse when we want tominimize the labor costs. Most of the workers’ working time is spent with travelingbetween source and destination points which cause deadheading. Even if a worker knowsthe structure of a warehouse well and because of that he or she can find the shortest pathbetween two points, it is still not guaranteed that there won’t be long traveling timebetween the locations of two consecutive tasks. We need optimal assignments betweentasks and workers.In the scientific literature Generalized Assignment Problem (GAP) is a wellknownproblem which deals with the assignment of m workers to n tasks consideringseveral constraints. The primary purpose of my thesis project was to choose a heuristics(genetic algorithm, tabu search or ant colony optimization) to be implemented into SAPExtended Warehouse Management (SAP EWM) by with task assignment will be moreeffective between tasks and resources.After system analysis I had to realize that due different constraints and businessdemands only 1:1 assingments are allowed in SAP EWM. Because of that I had to use adifferent and simpler approach – instead of the introduced heuristics – which could gainbetter assignments during the test phase in several cases. In the thesis I described indetails what ware the most important questions and problems which emerged during theplanning of my optimized assignment method.

Design/Evaluation of A Methodology For Performance Optimization Of Indexable Carbide Inserts

In this project, two broad facets in the design of a methodology for performance optimization of indexable carbide inserts were examined. They were physical destructive testing and software simulation.For the physical testing, statistical research techniques were used for the design of the methodology. A five step method which began with Problem definition, through System identification, Statistical model formation, Data collection and Statistical analyses and results was indepthly elaborated upon. Set-up and execution of an experiment with a compression machine together with roadblocks and possible solution to curb road blocks to quality data collection were examined. 2k factorial design was illustrated and recommended for process improvement. Instances of first-order and second-order response surface analyses were encountered. In the case of curvature, test for curvature significance with center point analysis was recommended. Process optimization with method of steepest ascent and central composite design or process robustness studies of response surface analyses were also recommended.For the simulation test, AdvantEdge program was identified as the most used software for tool development. Challenges to the efficient application of this software were identified and possible solutions proposed. In conclusion, software simulation and physical testing were recommended to meet the objective of the project.

Production and Delivery (Optimization of production system and reliability)

This thesis is done to solve two issues for Sayid Paper Mill Ltd Pakistan. Section one deals with a practical problem arise in SPM that is cutting a given set of raw paper rolls of known length and width, and a set of product paper rolls of known length (equal to the length of raw paper rolls) and width, practical cutting constraints on a single cutting machine, according to demand orders for all customers. To solve this problem requires to determine an optimal cutting schedule to maximize the overall cutting process profitability while satisfying all demands and cutting constraints. The aim of this part of thesis is to develop a mathematical model which solves this problem.Second section deals with a problem of delivering final product from warehouse to different destinations by finding shortest paths. It is an operational routing problem to decide the daily routes for sending trucks to different destination to deliver their final product. This industrial problem is difficult and includes aspect such as delivery to a single destination and multiple destinations with limited resources. The aim of this part of thesis is to develop a process which helps finding shortest path.

INVENTORY CONTROL SYSTEM : Optimization of production system and reliability

The main idea of this research to solve the problem of inventory management for the paper industry SPM PVT limited. The aim of this research was to find a methodology by which the inventory of raw material could be kept at minimum level by means of buffer stock level.The main objective then lies in finding the minimum level of buffer stock according to daily consumption of raw material, finding the Economic Order Quantity (EOQ) reorders point and how much order will be placed in a year to control the shortage of raw material.In this project, we discuss continuous review model (Deterministic EOQ models) that includes the probabilistic demand directly in the formulation. According to the formula, we see the reorder point and the order up to model. The problem was tackled mathematically as well as simulation modeling was used where mathematically tractable solution was not possible.The simulation modeling was done by Awesim software for developing the simulation network. This simulation network has the ability to predict the buffer stock level based on variable consumption of raw material and lead-time. The data collection for this simulation network is taken from the industrial engineering personnel and the departmental studies of the concerned factory. At the end, we find the optimum level of order quantity, reorder point and order days.

Developing a Communication link between Agents and cross Platform IDE

The main objective of this thesis work is to develop communication link between Runrev Revolution (IDE) and JADE (Multi-Agent System) through Socket programming using TCP/IP layer. These two independent platforms are connected using socket programming technique. Socket programming is considered to be newly emerging technology among these two platforms, the work done in this thesis work is considered to be a prototype.A Graphical simulation model is developed by salixphere (Company in Hedemora) to simulate logistic problems using Runrev Revolution (IDE). The simulation software/program is called “BIOSIM”. The logistic problems are complex, and conventional optimization techniques are unlikely very successful. “BIOSIM” can demonstrate the graphical representation of logistic problems depending upon the problem domains. As this simulation model is developed in revolution programming language (Transcript) which is dynamically typed and English-like language, it is quite slow compared to other high level programming languages. The object of this thesis work is to add intelligent behaviour in graphical objects and develop communication link between Runrev revolution (IDE) and JADE (Multi-Agent System) using TCP/IP layers.The test shows the intelligent behaviour in the graphical objects and successful communication between Runrev Revolution (IDE) and JADE (Multi-Agent System).

From the Reliable and Unselfish to the Versatile and Independent : - desired qualities in two Swedish curricula

The process in which girls and boys are constructed and construct themselves to pupils takes place in a context where conceptions of “the good pupil” are distinctly manifested in national school documents. In different types of texts concerning school and education, the image of the pupil that society wants to create emerges. Documents from early childhood education up to university level prioritise qualities such as independence, initiative, accountability and freedom to make ones own choices. Qualities or competencies that are preferred during a certain period change as time passes and society develops. The idea of the democratic subject is not the same today as it was 25 years ago. The purpose of this article is to emphasise and compare different desired qualities described in two Swedish national curricula, competencies that pupils in the compulsory school are supposed to develop. The discussion encompasses the political ideas of the pupil during a period of twenty-five years in light of changes in Western societies during the last decades.

Acupuncture with manual and electrical stimulation for labour pain : a two month follow up of recollection of pain and birth experience.

BACKGROUND: In a previous randomised controlled trial we showed that acupuncture with a combination of manual- and electrical stimulation (EA) did not affect the level of pain, as compared with acupuncture with manual stimulation (MA) and standard care (SC), but reduced the need for other forms of pain relief, including epidural analgesia. To dismiss an under-treatment of pain in the trial, we did a long-term follow up on the recollection of labour pain and the birth experience comparing acupuncture with manual stimulation, acupuncture with combined electrical and manual stimulation with standard care. Our hypothesis was that despite the lower frequency of use of other pain relief, women who had received EA would make similar retrospective assessments of labour pain and the birth experience 2 months after birth as women who received standard care (SC) or acupuncture with manual stimulation (MA). METHODS: Secondary analyses of data collected for a randomised controlled trial conducted at two delivery wards in Sweden. A total of 303 nulliparous women with normal pregnancies were randomised to: 40 min of MA or EA, or SC without acupuncture. Questionnaires were administered the day after partus and 2 months later. RESULTS: Two months postpartum, the mean recalled pain on the visual analogue scale (SC: 70.1, MA: 69.3 and EA: 68.7) did not differ between the groups (SC vs MA: adjusted mean difference 0.8, 95 % confidence interval [CI] -6.3 to 7.9 and SC vs EA: mean difference 1.3 CI 95 % -5.5 to 8.1). Positive birth experience (SC: 54.3 %, MA: 64.6 % and EA: 61.0 %) did not differ between the groups (SC vs MA: adjusted Odds Ratio [OR] 1.8, CI 95 % 0.9 to 3.7 and SC vs EA: OR 1.4 CI 95 % 0.7 to 2.6). CONCLUSIONS: Despite the lower use of other pain relief, women who received acupuncture with the combination of manual and electrical stimulation during labour made the same retrospective assessments of labour pain and birth experience 2 months postpartum as those who received acupuncture with manual stimulation or standard care. TRIAL REGISTRATION: ClinicalTrials.gov: NCT01197950.

Optical Characterization and Optimization of Display Components : Some Applications to Liquid-Crystal-Based and Electrochromics-Based Devices

This dissertation is focused on theoretical and experimental studies of optical properties of materials and multilayer structures composing liquid crystal displays (LCDs) and electrochromic (EC) devices. By applying spectroscopic ellipsometry, we have determined the optical constants of thin films of electrochromic tungsten oxide (WOx) and nickel oxide (NiOy), the films’ thickness and roughness. These films, which were obtained at spattering conditions possess high transmittance that is important for achieving good visibility and high contrast in an EC device. Another application of the general spectroscopic ellipsometry relates to the study of a photo-alignment layer of a mixture of azo-dyes SD-1 and SDA-2. We have found the optical constants of this mixture before and after illuminating it by polarized UV light. The results obtained confirm the diffusion model to explain the formation of the photo-induced order in azo-dye films. We have developed new techniques for fast characterization of twisted nematic LC cells in transmissive and reflective modes. Our techniques are based on the characteristics functions that we have introduced for determination of parameters of non-uniform birefringent media. These characteristic functions are found by simple procedures and can be utilised for simultaneous determination of retardation, its wavelength dispersion, and twist angle, as well as for solving associated optimization problems. Cholesteric LCD that possesses some unique properties, such as bistability and good selective scattering, however, has a disadvantage – relatively high driving voltage (tens of volts). The way we propose to reduce the driving voltage consists of applying a stack of thin (~1µm) LC layers. We have studied the ability of a layer of a surface stabilized ferroelectric liquid crystal coupled with several retardation plates for birefringent color generation. We have demonstrated that in order to accomplish good color characteristics and high brightness of the display, one or two retardation plates are sufficient.

The importance of body-mass exponent optimization for evaluation of performance capability in cross-country skiing

Introduction Performance in cross-country skiing is influenced by the skier’s ability to continuously produce propelling forces and force magnitude in relation to the net external forces. A surrogate indicator of the “power supply” in cross-country skiing would be a physiological variable that reflects an important performance-related capability, whereas the body mass itself is an indicator of the “power demand” experienced by the skier. To adequately evaluate an elite skier’s performance capability, it is essential to establish the optimal ratio between the physiological variable and body mass. The overall aim of this doctoral thesis was to investigate the importance of body-mass exponent optimization for the evaluation of performance capability in cross-country skiing. Methods In total, 83 elite cross-country skiers (56 men and 27 women) volunteered to participate in the four studies. The physiological variables of maximal oxygen uptake (V̇O2max) and oxygen uptake corresponding to a blood-lactate concentration of 4 mmol∙l-1 (V̇O2obla) were determined while treadmill roller skiing using the diagonal-stride technique; mean oxygen uptake (V̇O2dp) and upper-body power output (Ẇ) were determined during double-poling tests using a ski-ergometer. Competitive performance data for elite male skiers were collected from two 15-km classical-technique skiing competitions and a 1.25-km sprint prologue; additionally, a 2-km double-poling roller-skiing time trial using the double-poling technique was used as an indicator of upper-body performance capability among elite male and female junior skiers. Power-function modelling was used to explain the race and time-trial speeds based on the physiological variables and body mass. Results The optimal V̇O2max-to-mass ratios to explain 15-km race speed were V̇O2max divided by body mass raised to the 0.48 and 0.53 power, and these models explained 68% and 69% of the variance in mean skiing speed, respectively; moreover, the 95% confidence intervals (CI) for the body-mass exponents did not include either 0 or 1. For the modelling of race speed in the sprint prologue, body mass failed to contribute to the models based on V̇O2max, V̇O2obla, and V̇O2dp. The upper-body power output-to-body mass ratio that optimally explained time-trial speed was Ẇ ∙ m-0.57 and the model explained 63% of the variance in speed. Conclusions The results in this thesis suggest that V̇O2max divided by the square root of body mass should be used as an indicator of performance in 15-km classical-technique races among elite male skiers rather than the absolute or simple ratio-standard scaled expression. To optimally explain an elite male skier’s performance capability in sprint prologues, power-function models based on oxygen-uptake variables expressed absolutely are recommended. Moreover, to evaluate elite junior skiers’ performance capabilities in 2-km double-poling roller-skiing time trials, it is recommended that Ẇ divided by the square root of body mass should be used rather than absolute or simple ratio-standard scaled expression of power output.

Comparison of treatment of incomplete abortion with misoprostol by physicians and midwives at district level in Uganda : a randomised controlled equivalence trial

BACKGROUND: Misoprostol is established for the treatment of incomplete abortion but has not been systematically assessed when provided by midwives at district level in a low-resource setting. We investigated the effectiveness and safety of midwives diagnosing and treating incomplete abortion with misoprostol, compared with physicians. METHODS: We did a multicentre randomised controlled equivalence trial at district level at six facilities in Uganda. Eligibility criteria were women with signs of incomplete abortion. We randomly allocated women with first-trimester incomplete abortion to clinical assessment and treatment with misoprostol either by a physician or a midwife. The randomisation (1:1) was done in blocks of 12 and was stratified for study site. Primary outcome was complete abortion not needing surgical intervention within 14-28 days after initial treatment. The study was not masked. Analysis of the primary outcome was done on the per-protocol population with a generalised linear-mixed effects model. The predefined equivalence range was -4% to 4%. The trial was registered at ClinicalTrials.gov, number NCT01844024. FINDINGS: From April 30, 2013, to July 21, 2014, 1108 women were assessed for eligibility. 1010 women were randomly assigned to each group (506 to midwife group and 504 to physician group). 955 women (472 in the midwife group and 483 in the physician group) were included in the per-protocol analysis. 452 (95·8%) of women in the midwife group had complete abortion and 467 (96·7%) in the physician group. The model-based risk difference for midwife versus physician group was -0·8% (95% CI -2·9 to 1·4), falling within the predefined equivalence range (-4% to 4%). The overall proportion of women with incomplete abortion was 3·8% (36/955), similarly distributed between the two groups (4·2% [20/472] in the midwife group, 3·3% [16/483] in the physician group). No serious adverse events were recorded. INTERPRETATION: Diagnosis and treatment of incomplete abortion with misoprostol by midwives is equally safe and effective as when provided by physicians, in a low-resource setting. Scaling up midwives' involvement in treatment of incomplete abortion with misoprostol at district level would increase access to safe post-abortion care. FUNDING: The Swedish Research Council, Karolinska Institutet, and Dalarna University.

The relative perceptual weight of two Swedish prosodic contrasts

Abstract. In addition to 9 vowel and 18 consonant phonemes, Swedish has three prosodic phonemic contrasts: word stress, quantity and tonal word accent. There are also examples of distinctive phrase or sentence stress, where a verb can be followed by either an unstressed preposition or a stressed particle. This study focuses on word level and more specifically on word stress and tonal word accent in disyllabic words. When making curriculums for second language learners, teachers are helped by knowing which phonetic or phonological features are more or less crucial for the intelligibility of speech and there are some structural and anecdotal evidence that word stress should play a more important role for intelligibility of Swedish, than the tonal word accent. The Swedish word stress is about prominence contrasts between syllables, mainly signaled by syllable duration, while the tonal word accent is signaled mainly by pitch contour. The word stress contrast, as in armen [´arːmən] ‘the arm’ - armén [ar´meːn] ‘the army’, the first word trochaic and the second iambic, is present in all regional varieties of Swedish, and realized with roughly the same acoustic cues, while the tonal word accent, as in anden [´anːdən] ‘the duck’ - anden [`anːdən] ‘the spirit’ is absent in some dialects (as well as in singing), and also signaled with a variety of tonal patterns depending on region. The present study aims at comparing the respective perceptual weight of the two mentioned contrasts. Two lexical decision tests were carried out where in total 34 native Swedish listeners should decide whether a stimulus was a real word or a non-word. Real words of all mentioned categories were mixed with nonsense words and words that were mispronounced with opposite stress pattern or opposite tonal word accent category. The results show that distorted word stress caused more non-word judgments and more loss, than distorted word accent. Our conclusion is that intelligibility of Swedish is more sensitive to distorted word stress pattern than to distorted tonal word accent pattern. This is in compliance with the structural arguments presented above, and also with our own intuition.

Women's acceptability of misoprostol treatment for incomplete abortion by midwives and physicians : secondary outcome analysis from a randomized controlled equivalence trial at district level in Uganda

OBJECTIVE: This study aimed to assess women´s acceptability of diagnosis and treatment of incomplete abortion with misoprostol by midwives, compared with physicians. METHODS: This was an analysis of secondary outcomes from a multi-centre randomized controlled equivalence trial at district level in Uganda. Women with first trimester incomplete abortion were randomly allocated to clinical assessment and treatment with misoprostol by a physician or a midwife. The randomisation (1:1) was done in blocks of 12 and stratified for health care facility. Acceptability was measured in expectations and satisfaction at a follow up visit 14-28 days following treatment. Analysis of women's overall acceptability was done using a generalized linear mixed-effects model with an equivalence range of -4% to 4%. The study was not masked. The trial is registered at ClinicalTrials.org, NCT 01844024. RESULTS: From April 2013 to June 2014, 1108 women were assessed for eligibility of which 1010 were randomized (506 to midwife and 504 to physician). 953 women were successfully followed up and included in the acceptability analysis. 95% (904) of the participants found the treatment satisfactory and overall acceptability was found to be equivalent between the two study groups. Treatment failure, not feeling calm and safe following treatment, experiencing severe abdominal pain or heavy bleeding following treatment, were significantly associated with non-satisfaction. No serious adverse events were recorded. CONCLUSIONS: Treatment of incomplete abortion with misoprostol by midwives and physician was highly, and equally, acceptable to women. TRIAL REGISTRATION: ClinicalTrials.gov NCT01844024.