On the unimolecular loss of acetylene from metastable C11H9]+ ions

Extensive ¹³C labelling experiments demonstrate that loss of acetylene from metastable [C₁₁H₉]⁺ ions is a complex process, which can be described quantitatively in terms of a four-parameter model. The major reaction path (77.8%) involves scrambling of all 11 carbon atoms. Insight into the reaction details is provided neither by the kinetic energy release associated with the reaction [C₁₁H₉]⁺ → [C₉H₇]⁺ + C₂H₂ nor by the analysis of the collisional activation mass spectra of the resulting [C₉H₇]⁺ ions.     

Efficiency of the second-harmonic generation with the zeroth-order bessel-profile beams in uniaxial crystals

We study the efficiency of the second-harmonic generation with the zeroth-order Bessel beam (SHGzoBB) in uniaxial crystals. We show that the conversion efficiency is always less than that of the second-harmonic generation with the Gaussian beam (SHGGB). The fundamental reason relies on the fact that the advantage associated with the ??nondiffractive?? nature of the Bessel beam is not sufficient to compensate the disadvantage of its wave-vector distribution. We show that the zeroth-order Bessel beam is not the optimum beam for the second-harmonic generation in uniaxial crystals.     

Quantum Algorithm for Hilbert's Tenth Problem

We explore in the framework of Quantum Computation the notion of Computability, which holds a central position in Mathematics and Theoretical Computer Science. A quantum algorithm for Hilbert's tenth problem, which is equivalent to the Turing halting problem and is known to be mathematically noncomputable, is proposed where quantum continuous variables and quantum adiabatic evolution are employed. If this algorithm could be physically implemented, as much as it is valid in principle—that is, if certain Hamiltonian and its ground state can be physically constructed according to the proposal—quantum computability would surpass classical computability as delimited by the Church—Turing thesis. It is thus argued that computability, and with it the limits of Mathematics, ought to be determined not solely by Mathematics itself but also by Physical Principles.     

Highly sensitive and selective room temperature NH3 gas microsensor using an ionic conductor (CuBr) film

A new ammonia gas microsensor was developed, based on the large resistance change of an ionic conductor (CuBr) film when exposed to low NH₃ concentrations. The detection is based on specific interactions between ammonia molecules contained in the gas atmosphere and mobile copper ions in the copper(I) bromide layer. The sensor is operating at ambient temperature and allows highly sensitive and specific ammonia detection. The sensor works at ammonia concentrations between 1 and 500 ppm. There are no significant cross-effects to acetylene and carbon monoxide and only a weak cross-sensitivity to hydrogen sulfide gas (200 ppm). The selectivity was experimentally compared with commercial tin dioxide sensors (TGS 826). The sensor fabrication is a simple process, allowing low cost device production.     

Loan and nonloan flows in the Australian interbank network

High-value transactions between banks in Australia are settled in the Reserve Bank Information and Transfer System (RITS) administered by the Reserve Bank of Australia. RITS operates on a real-time gross settlement (RTGS) basis and settles payments and transfers sourced from the SWIFT payment delivery system, the Austraclear securities settlement system, and the interbank transactions entered directly into RITS. In this paper, we analyse a dataset received from the Reserve Bank of Australia that includes all interbank transactions settled in RITS on an RTGS basis during five consecutive weekdays from 19 February 2007 inclusive, a week of relatively quiescent market conditions. The source, destination, and value of each transaction are known, which allows us to separate overnight loans from other transactions (nonloans) and reconstruct monetary flows between banks for every day in our sample. We conduct a novel analysis of the flow stability and examine the connection between loan and nonloan flows. Our aim is to understand the underlying causal mechanism connecting loan and nonloan flows. We find that the imbalances in the banks’ exchange settlement funds resulting from the daily flows of nonloan transactions are almost exactly counterbalanced by the flows of overnight loans. The correlation coefficient between loan and nonloan imbalances is about −0.9 on most days. Some flows that persist over two consecutive days can be highly variable, but overall the flows are moderately stable in value. The nonloan network is characterised by a large fraction of persistent flows, whereas only half of the flows persist over any two consecutive days in the loan network. Moreover, we observe an unusual degree of coherence between persistent loan flow values on Tuesday and Wednesday. We probe static topological properties of the Australian interbank network and find them consistent with those observed in other countries.     

N-phosphonio formamidine derivatives: Synthesis,characterization, X-ray crystal structures,and deprotonation reactions

A simple and efficient method for the preparation of N-phosphonio formamidine derivatives of the general formula [R”₂N?C(H)=N?P(R’)R₂]⁺X^? is described. The data recorded in solution and the single crystal X-ray studies revealed that these compounds are best described by the combination of the two mesomeric N-phosphonio formamidine [R”₂N?C(H)=N?P(R’)R₂]⁺ and iminium phosphazene [R”₂N=C(H)?N=P(R’)R₂]⁺ forms. Formamidine phosphorus ylides ⁱPr₂N?C(H)=N?P(CH₂)R₂ were prepared after addition of ^tBuLi at –78 °C from the corresponding N-phosphonio compounds. [(PhCN)₂Pd(Cl)₂] was reacted with ⁱPr₂N?C(H)=N?P(CH₂)ⁱPr₂ to form the dimeric complex [(ⁱPr₂N?C(H)=N?P(CH₂)ⁱPr₂)Pd(Cl)(μ-Cl)]₂ which was structurally characterized by X-ray analysis. The deprotonation reactions conducted on [ⁱPr₂N?C(H)=N?PPh₃]⁺X^? occurred via an intramolecular rearrangement to give the cyanamide compound ⁱPr₂N?C≡N and PPh₃; transient formation of the amino-phosphazene-carbene ⁱPr₂N?C?N=PPh₃ was not observed.