Theoretical Rationalization of the Singlet–Triplet Gap in OLEDs Materials: Impact of Charge-Transfer Character

New materials for OLED applications with low singlet–triplet energy splitting have been recently synthesized in order to allow for the conversion of triplet into singlet excitons (emitting light) via a Thermally Activated Delayed Fluorescence (TADF) process, which involves excited-states with a non-negligible amount of Charge-Transfer (CT). The accurate modeling of these states with Time-Dependent Density Functional Theory (TD-DFT), the most used method so far because of the favorable trade-off between accuracy and computational cost, is however particularly challenging. We carefully address this issue here by considering materials with small (high) singlet–triplet gap acting as emitter (host) in OLEDs and by comparing the accuracy of TD-DFT and the corresponding Tamm-Dancoff Approximation (TDA), which is found to greatly reduce error bars with respect to experiments thanks to better estimates for the lowest singlet–triplet transition. Finally, we quantitatively correlate the singlet–triplet splitting values with the extent of CT, using for it a simple metric extracted from calculations with double-hybrid functionals, that might be applied in further molecular engineering studies.

Explaining the intention-behaviour gap in gluten-free diet adherence: the moderating roles of habit and perceived behavioural control

Adherence to a strict gluten-free diet is the only treatment for coeliac disease. Nonetheless, many individuals with the disease struggle to achieve and maintain strict adherence. While the theory of planned behaviour is useful for predicting gluten-free diet adherence, an intention-behaviour gap remains. The aim of this study was to investigate the roles of habit and perceived behavioural control in moderating the intention-behaviour relationship in gluten-free diet adherence. A significant three-way interaction was found such that the association between intention and adherence was dependent on both perceived behavioural control and habit. Implications for both theory and intervention design are discussed.

Bridging the gap: early warning, gender and the responsibility to protect

Women, Peace and Security (WPS) scholars and practitioners have expressed reservations about the Responsibility to Protect (R2P) principle because of its popular use as a synonym for armed humanitarian intervention. On the other hand, R2P’s early failure to engage with and advance WPS efforts such as United Nations Security Council (UNSC) resolution 1325 (2000) has seen the perpetuation of limited roles ascribed to women in implementing the R2P principle. As a result, there has been a knowledge and practice gap between the R2P and WPS agendas, despite the fact that their advocates share common goals in relation to the prevention of atrocities and protection of populations. In this article we propose to examine just one of the potential avenues for aligning the WPS agenda and R2P principle in a way that is beneficial to both and strengthens the pursuit of a shared goal – prevention. We argue that the development and inclusion of gender-specific indicators – particularly economic, social and political discriminatory practices against women – has the potential to improve the capacity of early warning frameworks to forecast future mass atrocities.

A distributional analysis of the gender wage gap in Bangladesh

This article empirically investigates the gender wage gap in Bangladesh during the period 2005–2009. Applying unconditional quantile regression models, the article demonstrates that women are paid less than men throughout the wage distribution and the gap is higher at the lower end of the distribution. Discrimination against women is the primary determinant of the wage gap. The article also demonstrates that the observed gender wage gap is likely to be underestimated if we ignore selection in full-time employment. A number of policy implications are discussed.

BUILDING A DISCOURSE: BRIDGING THE GAP BETWEEN NEW MEDIA'S CONVERGENCE AND RHETORIC AND COMPOSITION'S MULTIMODALITY

My dissertation emphasizes the use of narrative structuralism and narrative theories about storytelling in order to build a discourse between the fields of New Media and Rhetoric and Composition. Propp's morphological analysis and the breaking down of stories into component pieces aides in the discussion of storytelling as it appears in and is mediated by digital and computer technologies. New Media and Rhetoric and Composition are aided by shared concerns for textual production and consumption. In using the notion of "kairotic reading" (KR), I show the interconnectedness and interdisciplinarity required in the development of pedagogy utilized to teach students to develop into reflective practitioners that are aware of their rhetorical surroundings and can made sound judgments concerning their own message generation and consumption in the workplace. KR is a transferable skill that is beneficial to students and teachers alike. The dissertation research utilizes theories of New Media and New Media-influenced practitioners, including Jenkins' theory of convergence, Bourdieu's notion of taste, Gee's term "semiotic domains," and Manovich's "modification." These theoretical pieces are combined in order to show how KR can be extended by convergent narrative practices. In order to build connections with New Media, the consideration and inclusion of Kress and van Leeuwen's multimodality, Selber's "reflective practitioners," and Selfe's definition of multimodal composing allow for a greater establishment of conversation order to create a richer conversation around the implications of metacognitive development and practitioner reflexivity with scholars in New Media. My research also includes analysis of two popular media franchises Deborah Harkness' A Discovery of Witches and Fox's Bones television series to show similarities and differences among convergence-linked and multimodal narratives. Lastly, I also provide example assignments that can be taken, further developed, and utilized in classrooms engaging in multimodal composing practices. This dissertation pushes consideration of New Media into the work already being performed by those in Rhetoric and Composition.

Designing intrinsically photostable low band gap polymers:a smart tool combining EPR spectroscopy and DFT calculations

A rapid and efficient method to identify the weak points of the complex chemical structure of low band gap (LBG) polymers, designed for efficient solar cells, when submitted to light exposure is reported. This tool combines Electron Paramagnetic Resonance (EPR) using the 'spin trapping method' coupled with density functional theory modelling (DFT). First, the nature of the short life-time radicals formed during the early-stages of photo-degradation processes are determined by a spin-trapping technique. Two kinds of short life-time radical (R and R′O) are formed after 'short-duration' illumination in an inert atmosphere and in ambient air, respectively. Second, simulation allows the identification of the chemical structures of these radicals revealing the most probable photochemical process, namely homolytical scission between the Si atom of the conjugated skeleton and its pendent side-chains. Finally, DFT calculations confirm the homolytical cleavage observed by EPR, as well as the presence of a group that is highly susceptible to photooxidative attack. Therefore, the synergetic coupling of a spin trapping method with DFT calculations is shown to be a rapid and efficient method for providing unprecedented information on photochemical mechanisms. This approach will allow the design of LBG polymers without the need to trial the material within actual solar cell devices, an often long and costly screening procedure.

Robust gap repair in the contractile ring ensures timely completion of cytokinesis

Cytokinesis in animal cells requires the constriction of an actomyosin contractile ring, whose architecture and mechanism remain poorly understood. We use laser microsurgery to explore the biophysical properties of constricting rings in Caenorhabditis elegans embryos. Laser cutting causes rings to snap open. However, instead of disintegrating, ring topology recovers and constriction proceeds. In response to severing, a finite gap forms and is repaired by recruitment of new material in an actin polymerization-dependent manner. An open ring is able to constrict, and rings repair from successive cuts. After gap repair, an increase in constriction velocity allows cytokinesis to complete at the same time as controls. Our analysis demonstrates that tension in the ring increases while net cortical tension at the site of ingression decreases throughout constriction and suggests that cytokinesis is accomplished by contractile modules that assemble and contract autonomously, enabling local repair of the actomyosin network. Consequently, cytokinesis is a highly robust process impervious to discontinuities in contractile ring structure.

The Terminal Value (TV) Performing in Firm Valuation: The Gap of Literature and Research Agenda

The uncertainty about the future of firms must be modeled and incorporated in the valuation of enterprises outside the explicit period of analysis, i.e., in the continuing or terminal value (TV). There is a multiplicity of factors that influence the TV of firms which are not being considered within current evaluation models. This aspect leads to the incurring of unrecoverable errors, thus leading to values of goodwill or bad will far away from the substantial value of intrinsic assets. As a consequence, the evaluation results will be presented markedly different from market values. There is no consensus in the scientific community about the method of computation of the TV as a forecast in an infinite horizon. The size of the terminal, or non-explicit period, assumed as infinite, is never called into question by scientific literature, or the probability of business bankruptcy. This paper aims to promote a study of the existing literature on the TV, to highlight the fragility of the evaluation models of companies that have been used by the academic community and by financial analysts, and to point out lines for future research to minimize these errors.

NEIGHBORHOOD PERCEPTION OF SAFETY AND THE MOBILITY GAP BETWEEN MEN AND WOMEN IN OLD AGE

Thesis (Master, Community Health & Epidemiology) -- Queen's University, 2016-10-02 21:02:07.735

Modifying the band gap and optical properties of Germanium nanowires by surface termination

Semiconductor nanowires, based on silicon (Si) or germanium (Ge) are leading candidates for many ICT applications, including next generation transistors, optoelectronics, gas and biosensing and photovoltaics. Key to these applications is the possibility to tune the band gap by changing the diameter of the nanowire. Ge nanowires of different diameter have been studied with H termination, but, using ideas from chemistry, changing the surface terminating group can be used to modulate the band gap. In this paper we apply the generalised gradient approximation of density functional theory (GGA-DFT) and hybrid DFT to study the effect of diameter and surface termination using –H, –NH2 and –OH groups on the band gap of (001), (110) and (111) oriented germanium nanowires. We show that the surface terminating group allows both the magnitude and the nature of the band gap to be changed. We further show that the absorption edge shifts to longer wavelength with the –NH2 and –OH terminations compared to the –H termination and we trace the origin of this effect to valence band modifications upon modifying the nanowire with –NH2 or –OH. These results show that it is possible to tune the band gap of small diameter Ge nanowires over a range of ca. 1.1 eV by simple surface chemistry.

Educación legal clínica y defensa de los derechos humanos : casos paradigmáticos del Grupo de Acciones Públicas –GAP–

...este libro es el resultado de la implementación de la educación legal clínica, evidenciando, de un lado, la importancia de involucrar en la formación de los estudiantes de Jurisprudencia el componente práctico, al llevar a escenarios reales la aplicación de los conocimientos adquiridos en su carrera, incluso en asuntos de orden transnacional, y de otro lado, la imperiosa necesidad de poner en marcha el ejercicio responsable de su profesión, comprometiéndose con la realidad social de nuestro país. Adicionalmente, este libro es una herramienta de aprendizaje para clínicas de interés público en formación, para universidades y organizaciones que buscan implementar la enseñanza clínica en sus programas, para las comunidades y sus líderes, y en general para quienes buscan la forma responsable de ayudar a la comunidad a partir de la aplicación de sus conocimientos jurídicos..."--presentación.

Effects of cAMP modulators during in vitro prematuration of bovine oocytes on gap junctional communication and embryo development potential.

2016

Avaliação, empregando simulação, da diferença na produtividade (yield gap) do milho em Minas Gerais.

2016