Chemical structural effects on γ-ray spectra of positron annihilation in fluorobenzenes

Spectra of ?-ray Doppler shifts for positron annihilation in benzene and its fluoro-derivatives are simulated using low energy plane wave positron (LEPWP) approximation. The results are compared with available measurements. It is found that the Doppler shifts in these larger aromatic compounds are dominated by the contributions of the valence electrons and that the LEPWP model overestimates the measurements by approximately 30%, in agreement with previous findings in noble gases and small molecules. It is further revealed that the halogen atoms not only switch the sign of the charges on carbon atoms that they bond to, but that they also polarize other C-H bonds in the molecule leading to a redistribution of the molecular electrostatic potentials. As a result, it is likely that the halogen atoms contribute more significantly to the annihilation process. The present study also suggests that, while the Doppler shifts are sensitive to the number of valence electrons in the molecules, they are less sensitive to the chemical structures of isomers that have the same numbers and type of atoms and, hence, the same numbers of electrons. Further investigation of this effect is warranted. © EDP Sciences, Società Italiana di Fisica, Springer-Verlag 2012.

Interpreting the near-infrared spectra of the 'golden standard' Type Ia supernova 2005cf

We present nine near-infrared (NIR) spectra of supernova (SN) 2005cf at epochs from -10 to +42d with respect to B-band maximum, complementing the existing excellent data sets available for this prototypical Type Ia SN at other wavelengths. The spectra show a time evolution and spectral features characteristic of normal Type Ia SNe, as illustrated by a comparison with SNe 1999ee, 2002bo and 2003du. The broad-band spectral energy distribution (SED) of SN 2005cf is studied in combined ultraviolet (UV), optical and NIR spectra at five epochs between ~8d before and ~10d after maximum light. We also present synthetic spectra of the hydrodynamic explosion model W7, which reproduce the key properties of SN 2005cf not only at UV-optical as previously reported, but also at NIR wavelengths. From the radiative-transfer calculations we infer that fluorescence is the driving mechanism that shapes the SED of SNe Ia. In particular, the NIR part of the spectrum is almost devoid of absorption features, and instead dominated by fluorescent emission of both iron-group material and intermediate-mass elements at pre-maximum epochs, and pure iron-group material after maximum light. A single P-Cygni feature of Mgii at early epochs and a series of relatively unblended Coii lines at late phases allow us to constrain the regions of the ejecta in which the respective elements are abundant. © 2012 The Authors Monthly Notices of the Royal Astronomical Society © 2012 RAS.

Multidimensional modelling of X-ray spectra for AGN accretion disc outflows - II

Highly ionized fast accretion disc winds have been suggested as an explanation for a variety of observed absorption and emission features in the X-ray spectra of active galactic nuclei. Simple estimates have suggested that these flows may be massive enough to carry away a significant fraction of the accretion energy and could be involved in creating the link between supermassive black holes and their host galaxies. However, testing these hypotheses, and quantifying the outflow signatures, requires high-quality theoretical spectra for comparison with observations. Here, we describe extensions of our Monte Carlo radiative transfer code that allow us to generate realistic theoretical spectra for a much wider variety of disc wind models than that was possible in our previous work. In particular, we have expanded the range of atomic physics simulated by the code so that L- and M-shell ions can now be included. We have also substantially improved our treatment of both ionization and radiative heating such that we are now able to compute spectra for outflows containing far more diverse plasma conditions. We present example calculations that illustrate the variety of spectral features predicted by parametrized outflow models and demonstrate their applicability to the interpretation of data by comparison with observations of the bright quasar PG1211+143. We find that the major features in the observed 2-10 keV spectrum of this object can be well reproduced by our spectra, confirming that it likely hosts a massive outflow. © 2010 The Authors. Journal compilation © 2010 RAS.

Modified Thomson spectrometer design for high energy, multi-species ion sources

A modification to the standard Thomson parabola spectrometer is discussed, which is designed to measure high energy (tens of MeV/nucleon), broad bandwidth spectra of multi-species ions accelerated by intense laser plasma interactions. It is proposed to implement a pair of extended, trapezoidal shaped electric plates, which will not only resolve ion traces at high energies, but will also retain the lower energy part of the spectrum. While a longer (along the axis of the undeflected ion beam direction) electric plate design provides effective charge state separation at the high energy end of the spectrum, the proposed new trapezoidal shape will enable the low energy ions to reach the detector, which would have been clipped or blocked by simply extending the rectangular plates to enhance the electrostatic deflection.

Sputtering of oxygen ice by low energy ions

Naturally occurring ices lie on both interstellar dust grains and on celestial objects, such as those in the outer Solar system. These ices are continuously subjected to irradiation by ions from the solar wind and/or cosmic rays, which modify their surfaces. As a result, new molecular species may form which can be sputtered off into space or planetary atmospheres. We determined the experimental values of sputtering yields for irradiation of oxygen ice at 10 K by singly (He+, C+, N+, O+ and Ar+) and doubly (C2 +, N2 + and O2 +) charged ions with 4 keV kinetic energy. In these laboratory experiments, oxygen ice was deposited and irradiated by ions in an ultra high vacuum chamber at low temperature to simulate the environment of space. The number of molecules removed by sputtering was observed by measurement of the ice thickness using laser interferometry. Preliminary mass spectra were taken of sputtered species and of molecules formed in the ice by temperature programmed desorption (TPD). We find that the experimental sputtering yields increase approximately linearly with the projectile ion mass (or momentum squared) for all ions studied. No difference was found between the sputtering yields for singly and doubly charged ions of the same atom within the experimental uncertainty, as expected for a process dominated by momentum transfer. The experimental sputter yields are in good agreement with values calculated using a theoretical model except in the case of oxygen ions. Preliminary studies have shown molecular oxygen as the dominant species sputtered and TPD measurements indicate ozone formation.

High-resolution electron energy-loss spectroscopy of Ba Ti O 3∕ Sr Ti O 3 multilayers

The dielectric properties of BaTiO3 thin films and multilayers are different from bulk materials because of nanoscale dimensions, interfaces, and stress-strain conditions. In this study, BaTiO3/SrTiO3 multilayers deposited on SrTiO3 substrates by pulsed laser deposition have been investigated by high-energy-resolution electron energy-loss spectroscopy. The fine structures in the spectra are discussed in terms of crystal-field splitting and the internal strain. The crystal-field splitting of the BaTiO3 thin layer is found to be a little larger than that of bulk BaTiO3, which has been interpreted by the presence of the internal strain induced by the misfit at the interface. This finding is consistent with the lattice parameters of the BaTiO3 thin layer determined by the selected area diffraction pattern. The near-edge structure of the oxygen K edge in BaTiO3 thin layers and in bulk BaTiO3 are simulated by first-principle self-consistent full multiple-scattering calculations. The results of the simulations are in a good agreement with the experimental results. Moreover, the aggregation of oxygen vacancies at the rough BaTiO3/SrTiO3 interface is indicated by the increased [Ti]/[O] element ratio, which dominates the difference of dielectric properties between BaTiO3 layer and bulk materials.

Constraining the physical properties of Type II-Plateau supernovae using nebular phase spectra

We present a study of the nebular phase spectra of a sample of Type II-Plateau supernovae with identified progenitors or restrictive limits. The evolution of line fluxes, shapes and velocities is compared within the sample, and interpreted by the use of a spectral synthesis code. The small diversity within the data set can be explained by strong mixing occurring during the explosion, and by recognizing that most lines have significant contributions from primordial metals in the H envelope, which dominates the total ejecta mass in these types of objects. In particular, when using the [O I] 6300, 6364 Å doublet for estimating the core mass of the star, care has to be taken to account for emission from primordial O in the envelope. Finally, a correlation between the Hα line width and the mass of 56Ni is presented, suggesting that higher energy explosions are associated with higher 56Ni production.

Gamma-ray Spectra and Enhancement Factors for Positron Annihilation with Core Electrons

Many-body theory is developed to calculate the γ spectra for positron annihilation in noble-gas atoms. Inclusion of electron-positron correlation effects and core annihilation gives spectra in excellent agreement with experiment [K. Iwata et al., Phys. Rev. Lett. 79, 39 (1997)]. The calculated correlation enhancement factors γnl for individual electron orbitals nl are found to scale with the ionization energy I_nl (in eV), as γnl=1+ √A/Inl+(B/I_nl)β, where A≈40  eV, B≈24  eV, and β≈2.3.

Bounds for the signless laplacian energy

The energy of a graph G is the sum of the absolute values of the eigenvalues of the adjacency matrix of G. The Laplacian (respectively, the signless Laplacian) energy of G is the sum of the absolute values of the differences between the eigenvalues of the Laplacian (respectively, signless Laplacian) matrix and the arithmetic mean of the vertex degrees of the graph. In this paper, among some results which relate these energies, we point out some bounds to them using the energy of the line graph of G. Most of these bounds are valid for both energies, Laplacian and signless Laplacian. However, we present two new upper bounds on the signless Laplacian which are not upper bounds for the Laplacian energy. © 2010 Elsevier Inc. All rights reserved.

The electronic spectra and the determination of the excited state geometry of 3A" propynal /|nby Chhiu-Tsu Lin. -- 260 St. Catharines, Ont. : [s. n.],

Impurity free eluission spectra of HCCCHO and DCCCHO have been rephotographed using the electronic-energy-exchange method with benzene as a carrier gas. The near ultraviolet spectra of ReeCHO and DCCCHO were photographed in a sorption under conditions of high resolution with absorption path lengths up to 100 meters. The emission and absorption spectra of Propynal resulting from 3 n 1 t 1\ - A excitation has been reanalyzed in som.e detail. Botrl of the eH out-of-plane wagging modes were found to have negative anharmonicity. A barrier height of 56.8/0.0 cm- 1 and a nonplanar oft , , equilibrium angle of 17 3 /30 are calculated for the V 10/ lJ 11 modes. The in-plane and out-of-plane v1. brational modes in the 3A." and 1a~. ' elec ronic states of Propynal were subjected to a normal coordinate treatment in the approximat :on of tIle Urey-Bradley force field. From the relative oscillator strengths of the trans1·t1·0ns connect i ng t he v ibrat1•0n1ess lA' , state and t,he V1· bron1·C 3· if levels of the A state, the differences in equilibrium configuration were evaluated from an approximate Franck-Condon analysis based on the ground state normal coordinates. As this treatment gave 512 possible geometrical structures for the upper state, it 4 was necessary to resort to a comparison of the observed and calculated moments of inertia along with chemical intuition to isolate the structure. A test of the correctness of the calculated structure change and the vibrational assignment was raade by evaluating the intensities of the inplane and out-oi-plane fundarnental, sequence, and cross sequellce transitions y the exact Franck-Condon method.

The vibrational spectra and the normal coordinate analysis of thiocarbonye halides /|nby C. R. Subramaniam. -- 260 St. Catharines, Ont. : [s. n.],

The infrared and the Raman spectra of eSelF has been obtained for the first time and has been analysed to give the in-plane normal vibrational frequencies of the molecule, in the ground state. A normal co-ordinate analysis has been carried out for the molecules CSF2, CSClF and eSel 2 using a Urey-Bradley type of potential function and the elements of the [L] matrix elements, the distribution of the potential energy in Urey-Bradley space, and the displacement vector diagrams for the normal modes of vibration for these molecules, have been obtained. The bond for~e constants obtained through the normal co-ordinate analysis, have given some interesting results. The stretching force constant, Kes ' varies markedly with halogen substitution and the force constants KeF and Keel also vary with substitution.

An analysis of the methyl rotation dynamics in the So (x' A) and T (a A) states of thioacetaldehyde from Pyrolysis jet spectra /

Jet-cooled, laser-induced phosphorescence excitation spectra (LIP) of thioacetaldehyde CH3CHS, CH3CDS, CD3CHS and CD3CDS have been observed over the region 15800 - 17300 cm"^ in a continuous pyrolysis jet. The vibronic band structure of the singlet-triplet n -* n* transition were attributed to the strong coupling of the methyl torsion and aldehydic hydrogen wagging modes . The vibronic peaks have been assigned in terms of two upper electronic state (T^) vibrations; the methyl torsion mode v^g, and the aldehydic hydrogen wagging mode v^^. The electronic origin O^a^ is unequivocally assigned as follows: CH3CHS (16294.9 cm"'' ), CH3CDS (16360.9 cm"'' ), CD3CHS (16299.7 cm"^ ), and CD3CDS (16367.2 cm"'' ). To obtain structural and dynamical information about the two electronic states, potential surfaces V(e,a) for the 6 (methyl torsion) and a (hydrogen wagging) motions were generated by ab initio quantum mechanical calculations with a 6-3 IG* basis in which the structural parameters were fully relaxed. The kinetic energy coefficients BQ(a,e) , B^(a,G) , and the cross coupling term B^(a,e) , were accurately represented as functions of the two active coordinates, a and 9. The calculations reveal that the molecule adopts an eclipsed conformation for the lower Sq electronic state (a=0°,e=0"') with a barrier height to internal rotation of 541.5 cm"^ which is to be compared to 549.8 cm"^ obtained from the microwave experiment. The conformation of the upper T^ electronic state was found to be staggered (a=24 . 68° ,e=-45. 66° ) . The saddle point in the path traced out by the aldehyde wagging motion was calculated to be 175 cm"^ above the equilibrium configuration. The corresponding maxima in the path taken by methyl torsion was found to be 322 cm'\ The small amplitude normal vibrational modes were also calculated to aid in the assignment of the spectra. Torsional-wagging energy manifolds for the two states were derived from the Hamiltonian H(a,e) which was solved variationally using an extended two dimensional Fourier expansion as a basis set. A torsionalinversion band spectrum was derived from the calculated energy levels and Franck-Condon factors, and was compared with the experimental supersonic-jet spectra. Most of the anomalies which were associated with the interpretation of the observed spectrum could be accounted for by the band profiles derived from ab initio SCF calculations. A model describing the jet spectra was derived by scaling the ab initio potential functions. The global least squares fitting generates a triplet state potential which has a minimum at (a=22.38° ,e=-41.08°) . The flatter potential in the scaled model yielded excellent agreement between the observed and calculated frequency intervals.

Distribution of excitation energy in photosynthesis: a study of heat loss, photo chemical activity and fluorescence emission in intact calls of cyanobacterium.

Photosynthetic state transitions were investigated in the cyanobacterium Synechococcus sp. PCC 6301 by studying fluorescence emission, heat loss, and PS I activity in intact cells brought to state 1 and state 2. 77K fluorescence emission spectra were modelled with a sum of 6 components corresponding to PBS, PS II, and PS I emissions. The modelled data showed a large decrease in PS II fluorescence accompanied with a small increase in the PS I fluorescence upon transition to state 2 for excitation wavelengths absorbed by both PBS and ChI ll.. The fluorescence changes seen with ChI .a. excitations do not support the predictions of the mobile PBS model of state transition in PBS-containing organisms. Measurements of heat loss from intact cells in the two states were similar for both ChI it. and PBS excitations over three orders of magnitude of laser flash intensity. This suggests that the PBS does not become decoupled from PS II in state 2 as proposed by the PBS detachment model of state transition in PBS-containing organisms. PS I activity measurements done on intact cells showed no difference in the two states, in contrast with the predictions of all of the existing models of state transitions. Based on these results a model for state transition In PBScontaining organisms is proposed, with a PS II photoprotectory function.

Phonon spectra and temperature variation of thermodynamic properties of fcc metals via Finnis-Sinclair type many body potentials: Sutton-Chen and improved Sutton-Chen models

Volume(density)-independent pair-potentials cannot describe metallic cohesion adequately as the presence of the free electron gas renders the total energy strongly dependent on the electron density. The embedded atom method (EAM) addresses this issue by replacing part of the total energy with an explicitly density-dependent term called the embedding function. Finnis and Sinclair proposed a model where the embedding function is taken to be proportional to the square root of the electron density. Models of this type are known as Finnis-Sinclair many body potentials. In this work we study a particular parametrization of the Finnis-Sinclair type potential, called the "Sutton-Chen" model, and a later version, called the "Quantum Sutton-Chen" model, to study the phonon spectra and the temperature variation thermodynamic properties of fcc metals. Both models give poor results for thermal expansion, which can be traced to rapid softening of transverse phonon frequencies with increasing lattice parameter. We identify the power law decay of the electron density with distance assumed by the model as the main cause of this behaviour and show that an exponentially decaying form of charge density improves the results significantly. Results for Sutton-Chen and our improved version of Sutton-Chen models are compared for four fcc metals: Cu, Ag, Au and Pt. The calculated properties are the phonon spectra, thermal expansion coefficient, isobaric heat capacity, adiabatic and isothermal bulk moduli, atomic root-mean-square displacement and Gr\"{u}neisen parameter. For the sake of comparison we have also considered two other models where the distance-dependence of the charge density is an exponential multiplied by polynomials. None of these models exhibits the instability against thermal expansion (premature melting) as shown by the Sutton-Chen model. We also present results obtained via pure pair potential models, in order to identify advantages and disadvantages of methods used to obtain the parameters of these potentials.

Excitation wavelength dependence of energy transfer in dye mixture doped polymer optical fibre preforms

Dependence of energy transfer parameters on excitation wavelength has been investigated in poly (methyl methacrylate) (PMMA) optical fibre preforms doped with C 540:Rh B dye mixture by studying the fluorescence intensity and the lifetime variations. A fluorescence spectrophotometer was used to record the excitation spectra of the samples for the emission wavelengths 495 and 580 nm. The fluorescence emission from the polymer rods was studied at four specific excitation wavelengths viz; 445, 465, 488 and 532 nm. The fluorescence lifetime of the donor molecule was experimentally measured in polymer matrix by time correlated single photon counting technique. The energy transfer rate constants and transfer efficiencies were calculated and their dependence on the acceptor concentration was analysed for three excitation wavelengths. It was found that any change in the excitation wavelength leads to significant variations in the quenching characteristics, which in turn affect the calculated energy transfer parameters.