Spin-dependent charge recombination along para-phenylene molecular wires

We have used an efficient new quantum mechanical method for radical pair recombination reactions to study the spin-dependent charge recombination along PTZ$^{\bullet+}$--Ph$_n$--PDI$^{\bullet-}$ molecular wires. By comparing our results to the experimental data of E. Weiss {\em et al.} [J. Am. Chem. Soc. {\bf 126}, 5577 (2004)], we are able to extract the spin-dependent (singlet and triplet) charge recombination rate constants for wires with $n=2-5$. These spin-dependent rate constants have not been extracted previously from the experimental data because they require fitting its magnetic field-dependence to the results of quantum spin dynamics simulations. We find that the triplet recombination rate constant decreases exponentially with the length of the wire, consistent with the superexchange mechanism of charge recombination. However, the singlet recombination rate constant is nearly independent of the length of the wire, suggesting that the singlet pathway is dominated by an incoherent hopping mechanism. A simple qualitative explanation for the different behaviours of the two spin-selective charge recombination pathways is provided in terms of Marcus theory. We also find evidence for a magnetic field-independent background contribution to the triplet yield of the charge recombination reaction, and suggest several possible explanations for it. Since none of these explanations is especially compelling given the available experimental evidence, and since the result appears to apply more generally to other molecular wires, we hope that this aspect of our study will stimulate further experimental work.Comment: 12 pages, 10 figure

Asymmetric recombination and electron spin relaxation in the semiclassical theory of radical pair reactions

We describe how the semiclassical theory of radical pair recombination reactions recently introduced by two of us [D. E. Manolopoulos and P. J. Hore, J. Chem. Phys. 139, 124106 (2013)] can be generalised to allow for different singlet and triplet recombination rates. This is a non-trivial generalisation because when the recombination rates are different the recombination process is dynamically coupled to the coherent electron spin dynamics of the radical pair. Furthermore, because the recombination operator is a two-electron operator, it is no longer sufficient simply to consider the two electrons as classical vectors: one has to consider the complete set of 16 two-electron spin operators as independent classical variables. The resulting semiclassical theory is first validated by comparison with exact quantum mechanical results for a model radical pair containing 12 nuclear spins. It is then used to shed light on the spin dynamics of a carotenoid-porphyrin-fullerene (CPF) triad containing considerably more nuclear spins which has recently been used to establish a 'proof of principle' for the operation of a chemical compass [K. Maeda et al., Nature 453, 387 (2008)]. We find in particular that the intriguing biphasic behaviour that has been observed in the effect of an Earth-strength magnetic field on the time-dependent survival probability of the photo-excited C+PF- radical pair arises from a delicate balance between its asymmetric recombination and the relaxation of the electron spin in the carotenoid radical

The Limits of Liability: Can Alaska Oil Spill Victims Recover Pure Economic Loss

I denna rapport jämförs två olika metoder för att ta fram en modell för att kunna reglera en DC-motor med lead-lagreglering. I den ena metoden identifieras två parametrar i en given modell av andra ordningen, medan i den andra metoden skattas ett antal punkter i ett bodediagram direkt med hjälp av frekvensanalys. Resultaten indikerar att de två metoderna är ungefär likvärdiga för den process som studerats

Continued monitoring of LMXBs with the Faulkes Telescopes

The Faulkes Telescope Project is an educational and research arm of the Las Cumbres Observatory Global Telescope Network (LCOGTN). It has two 2-metre robotic telescopes, located at Haleakala on Maui (FT North) and Siding Spring in Australia (FT South). It is planned for these telescopes to be complemented by a research network of eighteen 1-metre telescopes, along with an educational network of twenty-eight 0.4-metre telescopes, providing 24 hour coverage of both northern and southern hemispheres. We have been conducting a monitoring project of 13 low-mass X-ray binaries (LMXBs) using FT North since early 2006. The introduction of FT South has allowed us to extend this to monitor a total of 30 LMXBs (see target list, Section 4). New instrumentation will allow us to expand this project to include both infrared wavelengths (z and y band) and spectroscopy. Brighter targets (~ 16 - 18 mag.) are imaged weekly in V, R and i’ bands (SNR ~ 50), while fainter ones (> 18 mag.) are observed only in i’ band (SNR ~ 20). We alter this cadence in response to our own analysis or Astronomers Telegrams (ATels)

Experiences in Integrated Multi-Domain Service Management

Increased competition, complex service provision chains and integrated service offerings require effective techniques for the rapid integration of telecommunications services and management systems over multiple organisational domains. This paper presents some of the results of practical development work in this area, detailing the technologies and standards used, the architectural approach taken and the application of this approach to specific services. This work covers the integration of multimedia services, broadband networks, service management and network management, though the detailed examples given focus specifically on the integration of services and service management

The Cyclic Connectivity of Homogeneous Arcwise Connected Continua

A continuum is cyclicly connected provided each pair of its points lie together on some simple closed curve. In 1927, G. T. Whyburn proved that a locally connected plane continuum is cyclicly connected if and only if it contains no separating points. This theorem was fundamental in his original treatment of cyclic element theory. Since then numerous authors have obtained extensions of Whyburn\u27s theorem. In this paper we characterize cyclic connectedness in the class of all Hausdorff continua