Ligand rigidity steers the selectivity and efficiency of the photosubstitution reaction of strained ruthenium polypyridyl complexes

While photosubstitution reactions in metal complexes are usually thought of as dissociative processes poorly dependent on the environment, they are, in fact, very sensitive to solvent effects. Therefore, it is crucial to explicitly consider solvent molecules in theoretical models of these reactions. Here, we experimentally and computationally investigated the selectivity of the photosubstitution of diimine chelates in a series of sterically strained ruthenium(II) polypyridyl complexes in water and acetonitrile. The complexes differ essentially by the rigidity of the chelates, which strongly influenced the observed selectivity of the photosubstitution. As the ratio between the different photoproducts was also influenced by the solvent, we developed a full density functional theory modeling of the reaction mechanism that included explicit solvent molecules. Three reaction pathways leading to photodissociation were identified on the triplet hypersurface, each characterized by either one or two energy barriers. Photodissociation in water was promoted by a proton transfer in the triplet state, which was facilitated by the dissociated pyridine ring acting as a pendent base. We show that the temperature variation of the photosubstitution quantum yield is an excellent tool to compare theory with experiments. An unusual phenomenon was observed for one of the compounds in acetonitrile, for which an increase in temperature led to a surprising decrease in the photosubstitution reaction rate. We interpret this experimental observation based on complete mapping of the triplet hypersurface of this complex, revealing thermal deactivation to the singlet ground state through intersystem crossing.NWOMetals in Catalysis, Biomimetics & Inorganic MaterialsSolid state NMR/Biophysical Organic Chemistr

Exact Hypersurface-Homogeneous Solutions in Cosmology and Astrophysics

A framework is introduced which explains the existence and similarities of most exact solutions of the Einstein equations with a wide range of sources for the class of hypersurface-homogeneous spacetimes which admit a Hamiltonian formulation. This class includes the spatially homogeneous cosmological models and the astrophysically interesting static spherically symmetric models as well as the stationary cylindrically symmetric models. The framework involves methods for finding and exploiting hidden symmetries and invariant submanifolds of the Hamiltonian formulation of the field equations. It unifies, simplifies and extends most known work on hypersurface-homogeneous exact solutions. It is shown that the same framework is also relevant to gravitational theories with a similar structure, like Brans-Dicke or higher-dimensional theories.Comment: 41 pages, REVTEX/LaTeX 2.09 file (don't use LaTeX2e !!!) Accepted for publication in Phys. Rev.

Electron Scattering From High-Momentum Neutrons in Deuterium

We report results from an experiment measuring the semi-inclusive reaction $d(e,e'p_s)$ where the proton $p_s$ is moving at a large angle relative to the momentum transfer. If we assume that the proton was a spectator to the reaction taking place on the neutron in deuterium, the initial state of that neutron can be inferred. This method, known as spectator tagging, can be used to study electron scattering from high-momentum (off-shell) neutrons in deuterium. The data were taken with a 5.765 GeV electron beam on a deuterium target in Jefferson Laboratory's Hall B, using the CLAS detector. A reduced cross section was extracted for different values of final-state missing mass $W^{*}$, backward proton momentum $\vec{p}_{s}$ and momentum transfer $Q^{2}$. The data are compared to a simple PWIA spectator model. A strong enhancement in the data observed at transverse kinematics is not reproduced by the PWIA model. This enhancement can likely be associated with the contribution of final state interactions (FSI) that were not incorporated into the model. A ``bound neutron structure function'' $F_{2n}^{eff}$ was extracted as a function of $W^{*}$ and the scaling variable $x^{*}$ at extreme backward kinematics, where effects of FSI appear to be smaller. For $p_{s}>400$ MeV/c, where the neutron is far off-shell, the model overestimates the value of $F_{2n}^{eff}$ in the region of $x^{*}$ between 0.25 and 0.6. A modification of the bound neutron structure function is one of possible effects that can cause the observed deviation.Comment: 33 pages RevTeX, 9 figures, to be submitted to Phys. Rev. C. Fixed 1 Referenc

eta-prime photoproduction on the proton for photon energies from 1.527 to 2.227 GeV

Differential cross sections for the reaction gamma p -> eta-prime p have been measured with the CLAS spectrometer and a tagged photon beam with energies from 1.527 to 2.227 GeV. The results reported here possess much greater accuracy than previous measurements. Analyses of these data indicate for the first time the coupling of the etaprime N channel to both the S_11(1535) and P_11(1710) resonances, known to couple strongly to the eta N channel in photoproduction on the proton, and the importance of j=3/2 resonances in the process.Comment: 6 pages, 3 figure

Measurement of the Deuteron Structure Function F2 in the Resonance Region and Evaluation of Its Moments

Inclusive electron scattering off the deuteron has been measured to extract the deuteron structure function F2 with the CEBAF Large Acceptance Spectrometer (CLAS) at the Thomas Jefferson National Accelerator Facility. The measurement covers the entire resonance region from the quasi-elastic peak up to the invariant mass of the final-state hadronic system W~2.7 GeV with four-momentum transfers Q2 from 0.4 to 6 (GeV/c)^2. These data are complementary to previous measurements of the proton structure function F2 and cover a similar two-dimensional region of Q2 and Bjorken variable x. Determination of the deuteron F2 over a large x interval including the quasi-elastic peak as a function of Q2, together with the other world data, permit a direct evaluation of the structure function moments for the first time. By fitting the Q2 evolution of these moments with an OPE-based twist expansion we have obtained a separation of the leading twist and higher twist terms. The observed Q2 behaviour of the higher twist contribution suggests a partial cancellation of different higher twists entering into the expansion with opposite signs. This cancellation, found also in the proton moments, is a manifestation of the "duality" phenomenon in the F2 structure function

First measurement of direct f0(980)f_0(980) photoproduction on the proton

We report on the results of the first measurement of exclusive $f_0(980)$ meson photoproduction on protons for $E_\gamma=3.0 - 3.8$ GeV and $-t = 0.4-1.0$ GeV$^2$. Data were collected with the CLAS detector at the Thomas Jefferson National Accelerator Facility. The resonance was detected via its decay in the $\pi^+ \pi^-$ channel by performing a partial wave analysis of the reaction $\gamma p \to p \pi^+ \pi^-$. Clear evidence of the $f_0(980)$ meson was found in the interference between $P$ and $S$ waves at $M_{\pi^+ \pi^-}\sim 1$ GeV. The $S$-wave differential cross section integrated in the mass range of the $f_0(980)$ was found to be a factor of 50 smaller than the cross section for the $\rho$ meson. This is the first time the $f_0(980)$ meson has been measured in a photoproduction experiment

A Bayesian analysis of pentaquark signals from CLAS data

We examine the results of two measurements by the CLAS collaboration, one of which claimed evidence for a $\Theta^{+}$ pentaquark, whilst the other found no such evidence. The unique feature of these two experiments was that they were performed with the same experimental setup. Using a Bayesian analysis we find that the results of the two experiments are in fact compatible with each other, but that the first measurement did not contain sufficient information to determine unambiguously the existence of a $\Theta^{+}$. Further, we suggest a means by which the existence of a new candidate particle can be tested in a rigorous manner.Comment: 5 pages, 3 figure

The Science of Sungrazers, Sunskirters, and Other Near-Sun Comets

This review addresses our current understanding of comets that venture close to the Sun, and are hence exposed to much more extreme conditions than comets that are typically studied from Earth. The extreme solar heating and plasma environments that these objects encounter change many aspects of their behaviour, thus yielding valuable information on both the comets themselves that complements other data we have on primitive solar system bodies, as well as on the near-solar environment which they traverse. We propose clear definitions for these comets: We use the term near-Sun comets to encompass all objects that pass sunward of the perihelion distance of planet Mercury (0.307 AU). Sunskirters are defined as objects that pass within 33 solar radii of the Sun’s centre, equal to half of Mercury’s perihelion distance, and the commonly-used phrase sungrazers to be objects that reach perihelion within 3.45 solar radii, i.e. the fluid Roche limit. Finally, comets with orbits that intersect the solar photosphere are termed sundivers. We summarize past studies of these objects, as well as the instruments and facilities used to study them, including space-based platforms that have led to a recent revolution in the quantity and quality of relevant observations. Relevant comet populations are described, including the Kreutz, Marsden, Kracht, and Meyer groups, near-Sun asteroids, and a brief discussion of their origins. The importance of light curves and the clues they provide on cometary composition are emphasized, together with what information has been gleaned about nucleus parameters, including the sizes and masses of objects and their families, and their tensile strengths. The physical processes occurring at these objects are considered in some detail, including the disruption of nuclei, sublimation, and ionisation, and we consider the mass, momentum, and energy loss of comets in the corona and those that venture to lower altitudes. The different components of comae and tails are described, including dust, neutral and ionised gases, their chemical reactions, and their contributions to the near-Sun environment. Comet-solar wind interactions are discussed, including the use of comets as probes of solar wind and coronal conditions in their vicinities. We address the relevance of work on comets near the Sun to similar objects orbiting other stars, and conclude with a discussion of future directions for the field and the planned ground- and space-based facilities that will allow us to address those science topics

Phenotypic, cytogenetic and spike fertility characterization of a population of male-sterile triticale

Triticale (X Triticosecale Wittmack) is a good cereal for production of flour and feed. A segregating population of triticale was developed from a male-sterile (MS) plant. To determine whether this new source of male sterility in triticale is appropriate for use in breeding programs the expression of the male sterility phenotype was characterized through spike fertility, meiotic behavior, and pollen. Controlled crosses between male-sterile plants and control varieties male-fertile (MF) of triticale were also conducted, and cytological analyses were performed in the F2 and backcross plants. Plants with male-sterile phenotypes displayed reduced spike fertility when compared to plants with male-fertile phenotypes. Compared to male-fertile plants, male-sterile plants exhibited a lower percentage of normal meiotic cells, a reduced meiotic index and reduced pollen viability. The F2 plants had improved pollen fertility when compared to the male-sterile population; however there were no corresponding improvements in the percentage of normal meiotic cells or in the meiotic index. A single generation of backcrosses resulted in an improved meiotic index and increased pollen viability. However, no changes in the percentage of normal meiotic cells were observed. Meiotic instability, which was shown to be inheritable, was the likely cause of male sterility. Therefore, the use of this population in triticale breeding was considered to be inappropriate because it could promote or contribute to the maintenance of meiotic instability, which is commonly observed in this species

A First Search for coincident Gravitational Waves and High Energy Neutrinos using LIGO, Virgo and ANTARES data from 2007

We present the results of the first search for gravitational wave bursts associated with high energy neutrinos. Together, these messengers could reveal new, hidden sources that are not observed by conventional photon astronomy, particularly at high energy. Our search uses neutrinos detected by the underwater neutrino telescope ANTARES in its 5 line configuration during the period January - September 2007, which coincided with the fifth and first science runs of LIGO and Virgo, respectively. The LIGO-Virgo data were analysed for candidate gravitational-wave signals coincident in time and direction with the neutrino events. No significant coincident events were observed. We place limits on the density of joint high energy neutrino - gravitational wave emission events in the local universe, and compare them with densities of merger and core-collapse events.Comment: 19 pages, 8 figures, science summary page at http://www.ligo.org/science/Publication-S5LV_ANTARES/index.php. Public access area to figures, tables at https://dcc.ligo.org/cgi-bin/DocDB/ShowDocument?docid=p120000