Extended states in disordered doped polyacetylene chains

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

Electronic structure of polyacetylene with bonded oxygen

In this work we have studied the electronic structure of finite polyacetylene chains with structural oxygen-bonding models following data from 13C-NMR experiments. We have used a combination of Austin Method One and Hydrogenic Atoms in Molecules version 3 methods to perform geometric and spectroscopic calculations. Our results show that the electronically-active states are generally unaffected by the incorporation of oxygen. © 1992.

Electronic states of trans-polyacetylene, poly(p-phenylene vinylene) and sp-hybridised carbon species in amorphous hydrogenated carbon probed by resonant Raman scattering

Inclusions of sp-hybridised, trans-polyacetylene [trans-(CH)x] and poly(p-phenylene vinylene) (PPV) chains are revealed using resonant Raman scattering (RRS) investigation of amorphous hydrogenated carbon (a-C:H) films in the near IR – UV range. The RRS spectra of trans-(CH)x core Ag modes and the PPV CC-H phenylene mode are found to transform and disperse as the laser excitation energy ћωL is increased from near IR through visible to UV, whereas sp-bonded inclusions only become evident in UV. This is attributed to ћωL probing of trans-(CH)x chain inhomogeneity and the distribution of chains with varying conjugation length; for PPV to the resonant probing of phelynene ring disorder; and for sp segments, to ћωL probing of a local band gap of end-terminated polyynes. The IR spectra analysis confirmed the presence of sp, trans-(CH)x and PPV inclusions. The obtained RRS results for a-C:H denote differentiation between the core Ag trans-(CH)x modes and the PPV phenylene mode. Furthermore, it was found that at various laser excitation energies the changes in Raman spectra features for trans-(CH)x segments included in an amorphous carbon matrix are the same as in bulk trans-polyacetylene. The latter finding can be used to facilitate identification of trans-(CH)x in the spectra of complex carbonaceous materials.

Low-lying states of transverse substituted trans-polyacetylene and trans-polyacetylene: A comparative DMRG study

The density-matrix renormalization group (DMRG) method is used for a comparative study of low-lying excitations in trans-polyacetylene (t-PA) and transversely substituted t-PA (TS-t-PA). We have employed the Pariser-Parr-Pople model Hamiltonian which incorporates long-range electronic correlations to model these systems. We find some fundamental differences in the excited states of the t-PA and TS-t-PA. We find that the lowest two-photon allowed excited state in TS-t-PA is not made up of two triplet excitons and the gap to this state is nonzero even for undimerized chains in the thermodynamic limit. Contrary to earlier results for the Hubbard model, we find that the lowest two-photon state is always below the first optically allowed state in all the systems studied here making TS-t-PA systems only weakly fluorescent materials. Nonresonant tumbling averaged linear and third harmonic generation optic coefficients of TS-t-PA systems are also much smaller than that of t-PA.

A multiconfigurational time-dependent Hartree-Fock method for excited electronic states. II. Coulomb interaction effects in single conjugated polymer chains

Conjugated polymers have attracted considerable attention in the last few decades due to their potential for optoelectronic applications. A key step that needs optimisation is charge carrier separation following photoexcitation. To understand better the dynamics of the exciton prior to charge separation, we have performed simulations of the formation and dynamics of localised excitations in single conjugated polymer strands. We use a nonadiabatic molecular dynamics method which allows for the coupled evolution of the nuclear degrees of freedom and of multiconfigurational electronic wavefunctions. We show the relaxation of electron-hole pairs to form excitons and oppositely charged polaron pairs and discuss the modifications to the relaxation process predicted by the inclusion of the Coulomb interaction between the carriers. The issue of charge photogeneration in conjugated polymers in dilute solution is also addressed. (C) 2011 American Institute of Physics. [doi: 10.1063/1.3600404]

Soliton clusters inducing insulator-to-metal transition in polyacetylene: a Su-Schrieffer-Heeger model study

The Su-Schrieffer-Heeger (SSH) Hamiltonian has been one of most used models to study the electronic structure of polyacetylene (PA) chains. It has been reported in the literature that in the SSH framework a disordered soliton distribution can not produce a metallic regime. However, in this work (using the same SSH model and parameters) we show that this is possible. The necessary conditions for true metals (non-vanishing density of states and extended wavefunctions around the Fermi level) are obtained for soliton concentration higher than 6% through soliton segregation (clustering). These results are consistent with recent experimental data supporting disorder as an essential mechanism behind the high conductivity of conducting polymers. (C) 2001 Elsevier B.V. B.V. All rights reserved.

Dynamic capabilities and innovation in supply chains

Supply chain relationships between firms are increasingly important in terms of both competitiveness and developing dynamic capability to respond to rapid changes in the market. Innovation capacity both in firms and in supply chains is also integral to responding to dynamic markets and customer needs. This explorative research examines a sample of firms active in supply chain relationships in Australia, as a pilot study, to examine any linkages between firm dynamic capabilities and supply chains developing innovative capacity to meet competitive and market changes. Initial findings indicate that although firms focus on developing capabilities, particularly dynamic capabilities to innovate individually, these preliminary findings indicate little reliance on developing their supply chain innovation capacity. This study is the initial stage of more extensive research on this topic.

Extending knowledge management across the supply chains in the construction industry : knowledge sharing in construction supply chains

Supply chain management and knowledge management have emerged as two distinct business philosophies in the last decade. Both are making rapid inroads into the construction industry. The premise of this paper is that knowledge management would make it possible for all the trading partners in a supply chain to reap benefits. Current research in knowledge management in the construction industry is generally targeting those big organisations that are main contractors. This has restricted the scope of knowledge management, and limits the benefits to a few, rather than the whole industry. If the construction industry as a whole is to prosper and improve its productivity, strategies for knowledge management strategy at the industry level must be established. This paper argues the case for extending the scope of knowledge management across the full extent of the supply chain, and attempts to identify the benefits that may arise out of sharing knowledge across the supply chain.

Investigating the role of ICT in improving productivity in construction supply chains in Australian construction industry.

The Australian construction industry is a fragmented and profoundly competitive industry with high levels of subcontracting resulting in complex supply chain formations. Traditional methods and forms of communication are being proven as inefficient and losing their charm while participants face heavy volumes of communications that often occurs on a daily basis between trading partners in a supply chain on projects. Information Communication Technologies (ICT), due to their robustness and the ability to quickly disseminate data/information, have the capacity to address highlighted communication issues in a structured and an efficient manner. Timesavings produced by these can be directly translated in terms of productivity gain. This paper presents perceptions of subcontractors working in the construction industry in Melbourne Australia on the use of ICT obtained through an exploratory study.

Labour rights as human rights : workers' safety at work in Australian-based supply chains

The increase of buyer-driven supply chains, outsourcing and other forms of non-traditional employment has resulted in challenges for labour market regulation. One business model which has created substantial regulatory challenges is supply chains. The supply chain model involves retailers purchasing products from brand corporations who then outsource the manufacturing of the work to traders who contract with factories or outworkers who actually manufacture the clothing and textiles. This business model results in time and cost pressures being pushed down the supply chain which has resulted in sweatshops where workers systematically have their labour rights violated. Literally millions of workers work in dangerous workplaces where thousands are killed or permanently disabled every year. This thesis has analysed possible regulatory responses to provide workers a right to safety and health in supply chains which provide products for Australian retailers. This thesis will use a human rights standard to determine whether Australia is discharging its human rights obligations in its approach to combating domestic and foreign labour abuses. It is beyond this thesis to analyse Occupational Health and Safety (OHS) laws in every jurisdiction. Accordingly, this thesis will focus upon Australian domestic laws and laws in one of Australia’s major trading partners, the Peoples’ Republic of China (China). It is hypothesised that Australia is currently breaching its human rights obligations through failing to adequately regulate employees’ safety at work in Australian-based supply chains. To prove this hypothesis, this thesis will adopt a three- phase approach to analysing Australia’s regulatory responses. Phase 1 will identify the standard by which Australia’s regulatory approach to employees’ health and safety in supply chains can be judged. This phase will focus on analysing how workers’ rights to safety as a human right imposes a moral obligation on Australia to take reasonablely practicable steps regulate Australian-based supply chains. This will form a human rights standard against which Australia’s conduct can be judged. Phase 2 focuses upon the current regulatory environment. If existing regulatory vehicles adequately protect the health and safety of employees, then Australia will have discharged its obligations through simply maintaining the status quo. Australia currently regulates OHS through a combination of ‘hard law’ and ‘soft law’ regulatory vehicles. The first part of phase 2 analyses the effectiveness of traditional OHS laws in Australia and in China. The final part of phase 2 then analyses the effectiveness of the major soft law vehicle ‘Corporate Social Responsibility’ (CSR). The fact that employees are working in unsafe working conditions does not mean Australia is breaching its human rights obligations. Australia is only required to take reasonably practicable steps to ensure human rights are realized. Phase 3 identifies four regulatory vehicles to determine whether they would assist Australia in discharging its human rights obligations. Phase 3 then analyses whether Australia could unilaterally introduce supply chain regulation to regulate domestic and extraterritorial supply chains. Phase 3 also analyses three public international law regulatory vehicles. This chapter considers the ability of the United Nations Global Compact, the ILO’s Better Factory Project and a bilateral agreement to improve the detection and enforcement of workers’ right to safety and health.

Inexact uniformization method for computing transient distributions of Markov chains

The uniformization method (also known as randomization) is a numerically stable algorithm for computing transient distributions of a continuous time Markov chain. When the solution is needed after a long run or when the convergence is slow, the uniformization method involves a large number of matrix-vector products. Despite this, the method remains very popular due to its ease of implementation and its reliability in many practical circumstances. Because calculating the matrix-vector product is the most time-consuming part of the method, overall efficiency in solving large-scale problems can be significantly enhanced if the matrix-vector product is made more economical. In this paper, we incorporate a new relaxation strategy into the uniformization method to compute the matrix-vector products only approximately. We analyze the error introduced by these inexact matrix-vector products and discuss strategies for refining the accuracy of the relaxation while reducing the execution cost. Numerical experiments drawn from computer systems and biological systems are given to show that significant computational savings are achieved in practical applications.

Reconfiguration or innovation in supply chains?

This research explores supply chain competitiveness and dynamic capabilities. It examines a pilot group of Australian supply chain organisations to understand the importance of dynamic capability in building innovation capacity for competitive advantage, and the concept of adopting a strategic approach to supply chain relationship building. A supply chain is after all a group of intra and interorganisational relationships delivering demand to end-users. This exploratory study confirms a positive relationship between the variables indicating both a strategic intent to develop relational capability, and very strong predictive linkages between the importance placed on developing supply chain dynamic capability and achieving supply chain innovation capacity as a competitive advantage.

Safety culture in supply chains : 'Customer is king'

Despite the presence of many regulations governing the operation of heavy vehicles and supply chains in Australia, the truck driving sector continues to have the highest incidence of fatal injuries compared to all other industries. The working environment has been the focus of attention by safety researchers during the past few decades, with particular consideration been given to the concept ‘safety culture’ and how to maintain, modify and advance responses to occupational risk. One important aspect of the heavy industry which sets it apart is the existence of cultural or sub-cultural influences at an industry wide and occupation-specific level rather than organisational level. This paper reports on the findings of stakeholder’s perceptions of the influences of power and control, and culture on industry safety. In-depth structured interviews were conducted during 2011 with Australian industry stakeholders (n=31). The questioning surrounded decision-making processes with regards to identifying risks, self-monitoring and reducing risky activities; as well as how power-affected relationships may influence the operational performance of supply chains and impacts on driver safety. One of the most significant findings from these interviews relates to the notion of power. The perception that the ‘Customer is King’ was widely viewed, with the majority of stakeholders believing that there exists a ‘master slave mentality’ in the industry. There appears to be great frustration in the industry as to the apparent immunity of customers (particularly retail supply chains) to their responsibilities. There was also a strong perception that the customer holds the balance of power by covertly employing remuneration-related incentives and pressures. Smaller trucking companies are perceived as being more vulnerable to the pressure of customer expectations.