Time-Dependent Density Functional Molecular Orbital and Excited State Calculations on Bis(porphyrinyl)butadiynes in the Monocationic, Neutral, Monoanionic, and Dianionic Oxidation States

We report a theoretical study of the multiple oxidation states (1+, 0, 1−, and 2−) of a meso,meso-linked diporphyrin, namely bis[10,15,20-triphenylporphyrinatozinc(II)-5-yl]butadiyne (4), using Time-Dependent Density Functional Theory (TDDFT). The origin of electronic transitions of singlet excited states is discussed in comparison to experimental spectra for the corresponding oxidation states of the close analogue bis{10,15,20-tris[3‘,5‘-di-tert-butylphenyl]porphyrinatozinc(II)-5-yl}butadiyne (3). The latter were measured in previous work under in situ spectroelectrochemical conditions. Excitation energies and orbital compositions of the excited states were obtained for these large delocalized aromatic radicals, which are unique examples of organic mixed-valence systems. The radical cations and anions of butadiyne-bridged diporphyrins such as 3 display characteristic electronic absorption bands in the near-IR region, which have been successfully predicted with use of these computational methods. The radicals are clearly of the “fully delocalized” or Class III type. The key spectral features of the neutral and dianionic states were also reproduced, although due to the large size of these molecules, quantitative agreement of energies with observations is not as good in the blue end of the visible region. The TDDFT calculations are largely in accord with a previous empirical model for the spectra, which was based simplistically on one-electron transitions among the eight key frontier orbitals of the C4 (1,4-butadiyne) linked diporphyrins.

Characterization of commercial double-walled carbon nanotube material : composition, structure, and heat capacity

A purified commercial double-walled carbon nanotube (DWCNT) sample was investigated by transmission electron microscopy (TEM), thermogravimetry (TG), and Raman spectroscopy. Moreover, the heat capacity of the DWCNT sample was determined by temperature-modulated differential scanning calorimetry in the range of temperature between -50 and 290 °C. The main thermo-oxidation characterized by TG occurred at 474 °C with the loss of 90 wt% of the sample. Thermo-oxidation of the sample was also investigated by high-resolution TG, which indicated that a fraction rich in carbon nanotube represents more than 80 wt% of the material. Other carbonaceous fractions rich in amorphous coating and graphitic particles were identified by the deconvolution procedure applied to the derivative of TG curve. Complementary structural data were provided by TEM and Raman studies. The information obtained allows the optimization of composites based on this nanomaterial with reliable characteristics.

Pedestrians Effects on Indoor MIMO-OFDM Channel Capacity

Temporal variations caused by pedestrian movement can significantly affect the channel capacity of indoor MIMOOFDM wireless systems. This paper compares systematic measurements of MIMO-OFDM channel capacity in presence of pedestrians with predicted MIMO-OFDM channel capacity values using geometric optics-based ray tracing techniques. Capacity results are presented for a single room environment using 5.2 GHz with 2x2, 3x3 and 4x4 arrays as well as a 2.45 GHz narrowband 8x8 MIMO array. The analysis shows an increase of up to 2 b/s/Hz on instant channel capacity with up to 3 pedestrians. There is an increase of up to 1 b/s/Hz in the average capacity of the 4x4 MIMO-OFDM channel when the number of pedestrians goes from 1 to 3. Additionally, an increment of up to 2.5 b/s/Hz in MIMO-OFDM channel capacity was measured for a 4x4 array compared to a 2x2 array in presence of pedestrians. Channel capacity values derived from this analysis are important in terms of understanding the limitations and possibilities for MIMO-OFDM systems in indoor populated environments.

Effect of Pedestrian Movement on MIMO-OFDM Channel Capacity in an Indoor Environment

Effects of pedestrian movement on multiple-input multiple-output orthogonal frequency division multiplexing (MIMO-OFDM) channel capacity have been investigated using experiment and simulation. The experiment was conducted at 5.2 GHz by a MIMO-OFDM packet transmission demonstrator using four transmitters and four receivers built in-house. Geometric optics based ray tracing technique was used to simulate the experimental scenarios. Changes in the channel capacity dynamic range have been analysed for different number of pedestrian (0-3) and antennas (2-4). Measurement and simulation results show that the dynamic range increases with the number of pedestrian and the number of antennas on the transmitter and receiver array.

Research monograph : emergence of smart urban ecosystems : application of ICT for capacity building in environmental decision making

Since the industrial revolution, our world has experienced rapid and unplanned industrialization and urbanization. As a result, we have had to cope with serious environmental challenges. In this context, explanation of how smart urban ecosystems can emerge, gains a crucial importance. Capacity building and community involvement have always been the key issues in achieving sustainable development and enhancing urban ecosystems. By considering these, this paper looks at new approaches to increase public awareness of environmental decision making. This paper will discuss the role of Information and Communication Technologies (ICT), particularly Web-based Geographic Information Systems (Web-based GIS) as spatial decision support systems to aid public participatory environmental decision making. The paper also explores the potential and constraints of these web-based tools for collaborative decision making.

Evaluation of functional performance in commercial buildings

This report fully summarises a project designed to enhance commercial real estate performance within both operational and investment contexts through the development of a model aimed at supporting improved decision-making. The model is based on a risk adjusted discounted cash flow, providing a valuable toolkit for building managers, owners, and potential investors for evaluating individual building performance in terms of financial, social and environmental criteria over the complete life-cycle of the asset. The ‘triple bottom line’ approach to the evaluation of commercial property has much significance for the administrators of public property portfolios in particular. It also has applications more generally for the wider real estate industry given that the advent of ‘green’ construction requires new methods for evaluating both new and existing building stocks. The research is unique in that it focuses on the accuracy of the input variables required for the model. These key variables were largely determined by market-based research and an extensive literature review, and have been fine-tuned with extensive testing. In essence, the project has considered probability-based risk analysis techniques that required market-based assessment. The projections listed in the partner engineers’ building audit reports of the four case study buildings were fed into the property evaluation model developed by the research team. The results are strongly consistent with previously existing, less robust evaluation techniques. And importantly, this model pioneers an approach for taking full account of the triple bottom line, establishing a benchmark for related research to follow. The project’s industry partners expressed a high degree of satisfaction with the project outcomes at a recent demonstration seminar. The project in its existing form has not been geared towards commercial applications but it is anticipated that QDPW and other industry partners will benefit greatly by using this tool for the performance evaluation of property assets. The project met the objectives of the original proposal as well as all the specified milestones. The project has been completed within budget and on time. This research project has achieved the objective by establishing research foci on the model structure, the key input variable identification, the drivers of the relevant property markets, the determinants of the key variables (Research Engine no.1), the examination of risk measurement, the incorporation of risk simulation exercises (Research Engine no.2), the importance of both environmental and social factors and, finally the impact of the triple bottom line measures on the asset (Research Engine no. 3).

The role of relational capabilities in developing the capacity for supply chain innovation

The purpose of this paper is to gain a better understanding of the types of relational capabilities supply chain participants develop to enable ongoing supply chain innovation capacity building that produces improved business outcomes. This is exploratory research using qualitative data gathered by using five interviews, with the Australian road freight industry as the context. Two key relational capabilities and the improvement of four key business outcomes were identified as being present in the interaction of freight transport service providers with members of their supply chain. The data also demonstrates that by entering into competence building relationships with customers and suppliers firms can build capabilities that will increase their capacity for supply chain innovation. Even in short term arm’s length relationships firms can acquire improved skills behaviours and practices that enhance their operation effectiveness and the efficiency of the supply chain relationships.

Poor functional health literacy : the silent disability for older people

In this information age, people are confronted by verbal, visual and written information. This is especially important in the health field, where information is needed to follow directions, understand prescriptions and undertake preventive behaviours. If provided in written form, much of this information may be inaccessible to people who cannot adequately read. Although poor literacy skills affect all groups in the population, older adults with fewer years of education seem to be particularly disadvantaged by an increasing reliance on written communication of health information. With older age comes a higher risk of illness and disability and a greater potential need to access the health system. As a result, poor literacy skills of older individuals may directly impact their health status. This paper explores the link between functional literacy and health, particularly for the older population, provides strategies to practitioners for the management of this problem, and suggests research initiatives in this area.

A framework for predicting the residual load carrying capacity of concrete structures exposed to aggressive environments

Reinforced concrete structures are susceptible to a variety of deterioration mechanisms due to creep and shrinkage, alkali-silica reaction (ASR), carbonation, and corrosion of the reinforcement. The deterioration problems can affect the integrity and load carrying capacity of the structure. Substantial research has been dedicated to these various mechanisms aiming to identify the causes, reactions, accelerants, retardants and consequences. This has improved our understanding of the long-term behaviour of reinforced concrete structures. However, the strengthening of reinforced concrete structures for durability has to date been mainly undertaken after expert assessment of field data followed by the development of a scheme to both terminate continuing degradation, by separating the structure from the environment, and strengthening the structure. The process does not include any significant consideration of the residual load-bearing capacity of the structure and the highly variable nature of estimates of such remaining capacity. Development of performance curves for deteriorating bridge structures has not been attempted due to the difficulty in developing a model when the input parameters have an extremely large variability. This paper presents a framework developed for an asset management system which assesses residual capacity and identifies the most appropriate rehabilitation method for a given reinforced concrete structure exposed to aggressive environments. In developing the framework, several industry consultation sessions have been conducted to identify input data required, research methodology and output knowledge base. Capturing expert opinion in a useable knowledge base requires development of a rule based formulation, which can subsequently be used to model the reliability of the performance curve of a reinforced concrete structure exposed to a given environment.