New insights from domain-averaged Fermi holes and bond order analysis into the bonding conundrum in C₂

The bonding in the ground state of C2 is examined using a combined approach based on the analysis of domain-averaged Fermi holes and of the contributions to covalent bond orders that can be associated with individual localised natural orbitals. The σ system in this molecule turns out to be particularly sensitive, evolving from a description that includes a fairly traditional shared electron pair σ bond, for a range of intermediate nuclear separations, to a somewhat different situation near equilibrium geometry, where non-classical repulsive interactions are particularly important. The various results provide further support for the view that the electronic structure of this molecule sufficiently exceeds the scope of traditional bonding paradigms that attempts to classify the bonding in terms of a classical bond multiplicity are highly questionable

Population Analysis of Pair Densities - A Study of Bassis Set Dependence

Based on work reported by several authors, one of us (RP) has introduced a Mulliken-like population analysis of pair densities. This scheme, introduced first at the semi-empirical level, was subsequently generalised both for SCF and for post-SCF ab initio methods. A potential problem is the basis set dependence that can be expected for all kinds of Mulliken-like approaches. The main purpose of the present study is to quantify this basis set dependence for a range of simple molecules, using basis sets ranging from STO-3Gto TZVP quality. It is shown, except for lowquality basis sets, that the »effective«pair populations derived from ab initio SCF calculations are relatively insensitive to the choice of basis set

Population Analysis of Pair Densities - A Study of Bassis Set Dependence

Based on work reported by several authors, one of us (RP) has introduced a Mulliken-like population analysis of pair densities. This scheme, introduced first at the semi-empirical level, was subsequently generalised both for SCF and for post-SCF ab initio methods. A potential problem is the basis set dependence that can be expected for all kinds of Mulliken-like approaches. The main purpose of the present study is to quantify this basis set dependence for a range of simple molecules, using basis sets ranging from STO-3Gto TZVP quality. It is shown, except for lowquality basis sets, that the »effective«pair populations derived from ab initio SCF calculations are relatively insensitive to the choice of basis set

Ab initio prediction of Boron compounds arising from Borozene: Structural and electronic properties

Structure and electronic properties of two unusual boron clusters obtained by fusion of borozene rings has been studied by means of first principles calculations, based on the generalized-gradient approximation of the density functional theory, and the semiempirical tight-binding method was used for the transport calculations. The role of disorder has also been considered with single vacancies and substitutional atoms. Results show that the pure boron clusters are topologically planar and characterized by (3c-2e) bonds, which can explain, together with the aromaticity (estimated by means of NICS), the remarkable cohesive energy values obtained. Such feature makes these systems competitive with the most stable boron clusters to date. On the contrary, the introduction of impurities compromises stability and planarity in both cases. The energy gap values indicate that these clusters possess a semiconducting character, while when the larger system is considered, zero-values of the density of states are found exclusively within the HOMO-LUMO gap. Electron transport calculations within the Landauer formalism confirm these indications, showing semiconductor-like low bias differential conductance for these stuctures. Differences and similarities with Carbon clusters are highlighted in the discussion.Comment: 10 pages, 2 tables, 5 figure

Multi-user video streaming using unequal error protection network coding in wireless networks

In this paper, we investigate a multi-user video streaming system applying unequal error protection (UEP) network coding (NC) for simultaneous real-time exchange of scalable video streams among multiple users. We focus on a simple wireless scenario where users exchange encoded data packets over a common central network node (e.g., a base station or an access point) that aims to capture the fundamental system behaviour. Our goal is to present analytical tools that provide both the decoding probability analysis and the expected delay guarantees for different importance layers of scalable video streams. Using the proposed tools, we offer a simple framework for design and analysis of UEP NC based multi-user video streaming systems and provide examples of system design for video conferencing scenario in broadband wireless cellular networks

Defining binding efficiency and specificity of auxins for SCF(TIR1/AFB)-Aux/IAA co-receptor complex formation.

Structure-activity profiles for the phytohormone auxin have been collected for over 70 years, and a number of synthetic auxins are used in agriculture. Auxin classification schemes and binding models followed from understanding auxin structures. However, all of the data came from whole plant bioassays, meaning the output was the integral of many different processes. The discovery of Transport Inhibitor-Response 1 (TIR1) and the Auxin F-Box (AFB) proteins as sites of auxin perception and the role of auxin as molecular glue in the assembly of co-receptor complexes has allowed the development of a definitive quantitative structure-activity relationship for TIR1 and AFB5. Factorial analysis of binding activities offered two uncorrelated factors associated with binding efficiency and binding selectivity. The six maximum-likelihood estimators of Efficiency are changes in the overlap matrixes, inferring that Efficiency is related to the volume of the electronic system. Using the subset of compounds that bound strongly, chemometric analyses based on quantum chemical calculations and similarity and self-similarity indices yielded three classes of Specificity that relate to differential binding. Specificity may not be defined by any one specific atom or position and is influenced by coulomb matrixes, suggesting that it is driven by electrostatic forces. These analyses give the first receptor-specific classification of auxins and indicate that AFB5 is the preferred site for a number of auxinic herbicides by allowing interactions with analogues having van der Waals surfaces larger than that of indole-3-acetic acid. The quality factors are also examined in terms of long-standing models for the mechanism of auxin binding

Prevention of catheter lumen occlusion with rT-PA versus heparin (Pre-CLOT): study protocol of a randomized trial [ISRCTN35253449]

BACKGROUND: Many patients with end-stage renal disease use a central venous catheter for hemodialysis access. A large majority of these catheters malfunction within one year of insertion, with up to two-thirds due to thrombosis. The optimal solution for locking the catheter between hemodialysis sessions, to decrease the risk of thrombosis and catheter malfunction, is unknown. The Prevention of Catheter Lumen Occlusion with rt-PA versus Heparin (PreCLOT) study will determine if use of weekly rt-PA, compared to regular heparin, as a catheter locking solution, will decrease the risk of catheter malfunction. METHODS/DESIGN: The study population will consist of patients requiring chronic hemodialysis thrice weekly who are dialyzed with a newly inserted permanent dual-lumen central venous catheter. Patients randomized to the treatment arm will receive rt-PA 1 mg per lumen once per week, with heparin 5,000 units per ml as a catheter locking solution for the remaining two sessions. Patients randomized to the control arm will receive heparin 5,000 units per ml as a catheter locking solution after each dialysis session. The study treatment period will be six months, with 340 patients to be recruited from 14 sites across Canada. The primary outcome will be catheter malfunction, based on mean blood flow parameters while on hemodialysis, with a secondary outcome of catheter-related bacteremia. A cost-effectiveness analysis will be undertaken to assess the cost of maintaining a catheter using rt-PA as a locking solution, compared to the use of heparin. DISCUSSION: Results from this study will determine if use of weekly rt-PA, compared to heparin, will decrease catheter malfunction, as well as assess the cost-effectiveness of these locking solutions