Chemical evolution of protoplanetary disks - the effects of viscous accretion, turbulent mixing and disk winds

We calculate the chemical evolution of protoplanetary disks considering radial viscous accretion, vertical turbulent mixing, and vertical disk winds. We study the effects on the disk chemical structure when different models for the formation of molecular hydrogen on dust grains are adopted. Our gas-phase chemistry is extracted from the UMIST Database for Astrochemistry (Rate06) to which we have added detailed gas-grain interactions. We use our chemical model results to generate synthetic near- and mid-infrared local thermodynamic equilibrium line emission spectra and compare these with recent Spitzer observations. Our results show that if H2 formation on warm grains is taken into consideration, the H2O and OH abundances in the disk surface increase significantly. We find that the radial accretion flow strongly influences the molecular abundances, with those in the cold midplane layers particularly affected. On the other hand, we show that diffusive turbulent mixing affects the disk chemistry in the warm molecular layers, influencing the line emission from the disk and subsequently improving agreement with observations. We find that NH3, CH3OH, C2H2, and sulfur-containing species are greatly enhanced by the inclusion of turbulent mixing. We demonstrate that disk winds potentially affect the disk chemistry and the resulting molecular line emission in a manner similar to that found when mixing is included.

Determination of higher heating value of petro-diesels using mid-infrared spectroscopy and chemometry

Higher heating value (HHV) is probably the most important property of the fuels. Bomb calorimeter and derived empirical formulae are often used for accurate determination of HHV of fuels. A useful empirical equation was derived to estimate HHV of petro-diesels from their C and H contents: HHV (in MJ/kg) = 0.3482(C) + 1.1887(H), r (2) = 0.9956. The derived correlation was validated against the most common formulae in the literature, Boie and Channiwala-Parikh correlations. Accordingly, accurate determination of C and H contents is essential for estimation of HHV and avoids using a bomb calorimeter. However, accurate estimation of C and H contents requires using expensive and laborious gas chromatographic techniques. In this work, chemometry offered a simple method for HHV determination of petro-diesels without using bomb calorimeter or even gas chromatography. PLS-1 calibration was used instead of gas chromatography to find C and H contents from the non-selective mid-infrared (MIR) spectra of petro-diesels, HHV was then estimated from the earlier empirical equation. The proposed method predicts HHV of petro-diesels with high accuracy and precision, with modest analysis costs. The present method may be extended to other fuels.

Role of low-energy electrons in Ar emission from low-pressure radio frequency discharge plasma

Optical emission spectra from a low-pressure Ar plasma were studied with high spatial resolution. It has been shown that the intensity ratios of Ar lines excited through metastable levels to those excited directly from the ground state are sensitive to the shape of electron energy distribution function. From these measurements, important information on the spatial variation of plasma parameters can be obtained. (C) 1999 American Institute of Physics. [S0003-6951(99)01629-0].

A Stubbornly Large Mass of Cold Dust in the Ejecta of Supernova 1987A

We present new Herschel photometric and spectroscopic observations of Supernova 1987A, carried out in 2012. Our dedicated photometric measurements provide new 70 mu m data and improved imaging quality at 100 and 160 mu m compared to previous observations in 2010. Our Herschel spectra show only weak CO line emission, and provide an upper limit for the 63 mu m [O-I] line flux, eliminating the possibility that line contaminations distort the previously estimated dustmass. The far-infrared spectral energy distribution (SED) is well fitted by thermal emission from cold dust. The newly measured 70 mu m flux constrains the dust temperature, limiting it to nearly a single temperature. The far-infrared emission can be fitted by 0.5 +/- 0.1M(circle dot) of amorphous carbon, about a factor of two larger than the current nucleosynthetic mass prediction for carbon. The observation of SiO molecules at early and late phases suggests that silicates may also have formed and we could fit the SED with a combination of 0.3M(circle dot) of amorphous carbon and 0.5M(circle dot) of silicates, totalling 0.8M(circle dot) of dust. Our analysis thus supports the presence of a large dust reservoir in the ejecta of SN 1987A. The inferred dust mass suggests that supernovae can be an important source of dust in the interstellar medium, from local to high-redshift galaxies.

The Unexpected Preference for the fac-Isomer with the Tris(5-ester-substituted-2,2′-bipyridine) Complexes of Ruthenium(II)

The synthesis of a number of new 2,2'-bipyridine ligands, functionalized with bulky ester side groups is reported (L2 - L8). Their reaction with [Ru(DMSO)4Cl2] gives rise to tris-chelate ruthenium(II) metal complexes which show an unusually high proportion of the fac-isomer, as judged by 1H NMR following conversion to the ruthenium(II) complex of 2,2'-bipyridine-5-carboxylic acid methyl ester (L1). The initial reaction appears to have thermodynamic control with the steric bulk of the ligands causing the third ligand to be labile under the reaction conditions used, giving rise to disappointing yields and allowing rearrangement to the more stable facial form. DFT studies indicate that this does not appear to be as a consequence of a metal centered electronic effect. The two isomers of [Ru(L1)3](PF6)2 were separated into the two individual forms using silica preparative plate chromatographic procedures, and the photophysical characteristics of the two forms compared. The results appear to indicate that there is no significant difference in both their room temperature electronic absorption and emission spectra or their excited state lifetimes at 77K.

Fully differential cross sections for transfer ionization - a sensitive probe of high level correlation effects in atoms

The transfer ionization process offers a unique opportunity to study radial and angular electron correlations in the helium atom. We report calculations for the multiple differential cross sections of the transfer ionization process p + He --> H + He++ + e(-). The results of these calculations demonstrate the strong sensitivity of the fully differential cross sections to fine details of electron correlation in the target atom. Specifically, angular electron correlation in the ground state of helium results in a broad peak in the electron emission spectra in the backward direction, relative to the incoming beam. Our model explains some of the key effects observed in measurements of multiple differential cross sections using the COLTRIMS technique.

Speciation of uranyl complexes in ionic liquids by optical spectroscopy

Uranyl complexes dissolved in room-temperature ionic liquids have diagnostic absorption and emission spectra which reflect the molecular symmetry and geometry. In particular, the characteristic vibrational fine structure of the absorption spectra allows identification of the molecular symmetry of a uranyl complex. The concept of speciation of. uranyl complexes is illustrated for the hydrated uranyl ion, the tetrachloro complex [UO2Cl4](2-), the trinitrato complex [UO2(NO3)(3)](-), the triacetato complex [UO2(CH3COO)(3)](-) and the crown ether complex [UO2(18-crown-6)](2+) in imidazolium and pyrrolidinium bis(trifluoromethylsulfonyl)imide ionic liquids. The competition between 18- crown-6 and small inorganic ligands for coordination to the uranyl ion was investigated. The crystal structures of the hydrolysis product [(UO2)(2)(mu(2)-OH)(2)(H2O)(6)] [UO2Br4](18-crown-6)(4) and imidazolium salt [C(6)mim](2)[UO2Br4] are described.

Electrical, Thermal and Optical Diagnostics of an Atmospheric Plasma Jet System

Plasma diagnostics of atmospheric plasmas is a key tool in helping to understand processing performance issues. This paper presents an electrical, optical and thermographic imaging study of the PlasmaStream atmospheric plasma jet system. The system was found to exhibit three operating modes; one constricted/localized plasma and two extended volume plasmas. At low power and helium flows the plasma is localized at the electrodes and has the electrical properties of a corona/filamentary discharge with electrical chaotic temporal structure. With increasing discharge power and helium flow the plasma expands into the volume of the tube, becoming regular and homogeneous in appearance. Emission spectra show evidence of atomic oxygen, nitric oxide and the hydroxyl radical production. Plasma activated gas temperature deduced from the rotational temperature of nitrogen molecules was found to be of order of 400 K: whereas thermographic imaging of the quartz tube yielded surface temperatures between 319 and 347 K.

Examination of the Silver Colloid Binding Behavior of Disulfide-Tethered Bipyridine Ligands and Their fac-Tricarbonylrhenium(I) Complexes

The syntheses of 2,2'-bipyridin-5-ylmethyl-5-(1,2-dithiolan-3-yl)pentanoate (L1) and N-(2,2'-bipyridin-5-ylmethyl)-5-(1,2-dithiolan-3-yl)pentanamide (L2) and their neutral fac carbonylrhenium(I) complexes [Re(L1)(CO)(3)Br] and [Re(L2)(CO)(3)Br] are reported. The. electronic absorption and emission spectra of the complexes are similar to the spectrum of the reference compound [Re(bipy)(CO)(3)Br] and correlate well with the density functional theory calculations undertaken. The surface-enhanced Raman spectroscopy (SERS) spectra (excited at both 532 and 785 nm) of the ligands and complexes were examined and compared to the spectrum of ethyl 5-(1,2-dithiolan-3-yl)pentanoate (L3), revealing that there is very little contribution to the spectra of these species from the dithiolated alkyl chains. The spectra are dominated by the characteristic peaks of a metalated 2,2'-bipyridyl group,arising from the silver colloid/ion complexation, and the rhenium center. The rhenium complexes show weak SERS bands related to the CO stretches and a broad band at 510 cm(-1) assigned to Re-CO stretching. Concentration dependent studies, measured by the relative intensity of several assigned peaks, indicate that, as the surface coverage increases, the bipyridine moiety lifts off the surface In the case of L1 and L2, this gives rise to complexes with silver at low concentration, enhancing the signals observed, while for the tricarbonylbromorhenium complexes of these ligands, the presence of the disulfide tether allows an enhancement in the limits of detection of these surface-borne species of 20 times in the case of [ReL2(CO)(3)Br] over [Re(bipy)(CO)(3)Br].

Alkynyl-Bridged Ruthenium(II) 4 '-Diferroceny1-2,2 ':6 ',2 ''-terpyridine Electron Transfer Complexes: Synthesis, Structures, and Electrochemical and Spectroscopic Studiese

The novel ligand 4'-diferrocenylallcyne-2,2':6',2 ''-terpyridine (7; Fc-C C-Fc-tpy; tpy = terpyridyl; Fc = ferrocenyl) and its Ru2+ complexes 8-10 have been synthesized and characterized by single-crystal X-ray diffraction, cyclic voltammetry, and UV-vis and luminescence spectroscopy. Electrochemical data and UV absorption and emission spectra indicate that the insertion of an ethynyl group causes delocalization of electrons in the extended pi* orbitals. Cyclic voltammetric measurements of 7 show two successive reversible one-electron-oxidation processes with half-wave potentials of 0.53 and 0.78 V. The small variations of the E-1/2 values for the Fe2+/Fe3+ redox couples after the coordination of the Ru2+ ion suggest a weak interaction between the Ru2+ and Fe2+ centers. After insertion of an ethynyl group, UV-vis absorption spectra show a red shift of the absorption peak of the (1)[(d(pi)(Fe))(6)]->(1)[(d(pi)(Fe))(5)(pi*(Ru)(tpy))(1)] MMLCT of the Ru2+ complexes. The Ru2+ complex 8 exhibits the strongest luminescence intensity (lambda(em)(max) 712 nm, Phi(em) = 2.63 x 10(-4), tau = 323 ns) relative to analogous ferrocene-based terpyridine Ru(II) complexes in H2O/CH3CN (4/1 v/v) solution.

Magnetic mirror cavities as terahertz radiation sources and a means of quantifying radiation friction

We propose a radiation source based on a magnetic mirror cavity. Relativistic electrons are simulated entering the cavity and their trajectories and resulting emission spectra are calculated. The uniformity of the particle orbits is found to result in a frequency comb in terahertz range, the precise energies of which are tunable by varying the electron's gamma-factor. For very high energy particles, radiation friction causes the spectral harmonics to broaden and we suggest this as a possible way to verify competing classical equations of motion.

Testing numerical implementations of strong-field electrodynamics

We test current numerical implementations of laser-matter interactions by comparison with exact analytical results. Focusing on photon emission processes, it is found that the numerics accurately reproduce analytical emission spectra in all considered regimes, except for the harmonic structures often singled out as the most significant high-intensity (multiphoton) effects. We find that this discrepancy originates in the use of the locally constant field approximation.

Photo-ionized neon plasmas induced by radiation pulses of a laser-plasma EUV source and a free electron laser FLASH

In this work, a laser-produced plasma extreme ultraviolet source and a free electron laser were used to create Ne photo-ionized plasmas. In both cases, a radiation beam was focused onto a gas stream injected into a vacuum chamber synchronously with the radiation pulse. Extreme ultraviolet radiation from the plasma spanned a wide spectral range with pronounced maximum centered at lambda = 11 +/- 1 nm while the free electron laser pulses were emitted at a wavelength of 32 nm. The power density of the focused plasma radiation was approximately 2 x 10(7) W/cm(2) and was seven orders of magnitude lower compared with the focused free electron laser beam. Radiation fluences in both experimental conditions were comparable. Despite quite different spectral characteristics and extremely different power densities, emission spectra of both photo-ionized plasmas consist of the same spectral lines within a wavelength range of 20 to 50 nm, however, with different relative intensities of the corresponding lines. The dominating spectral lines originated from singly charged ions (Ne II); however, Ne III lines were also detected. Additionally, computer simulations of the emission spectra, obtained for photo-ionized plasmas, driven by the plasma extreme ultraviolet source, were performed. The corresponding measured and calculated spectra are presented. An electron temperature and ionic composition were estimated. Differences between the experimental spectra, obtained for both irradiation conditions, were analyzed. The differences were attributed mainly to different energies of driving photons.

Effect of ultraviolet-B light on lymphocyte activity at doses at which normal bone marrow stem cells are preserved

Ultraviolet B (UVB) light is known to be immunosuppressive, but, probably because of a small UVC component in the emission spectra of some of the UVB lamps used, reports vary on effective dose levels. To prevent potentially lethal graft-versus-host disease (GVHD) after allogeneic bone marrow transplantation, alloreactive donor T-cell activity must be suppressed. In this study, a narrow wavelength UVB lamp (TL01, 312 nm peak emission) was used to determine what doses of UVB were required to abolish rat lymphocyte proliferation while simultaneously preserving rat bone marrow progenitor cell and primitive hematopoietic stem cell viability. Lymphocyte proliferation, as measured by 3H-Thymidine incorporation, in response to lectin stimulation was abolished below detection at doses greater than 3,500 J/m2. When T-cell clonogenicity was measured in a limiting dilution assay, a small fraction (0.6%) was maintained at doses up to 4,000 J/m2. Cytotoxic T-lymphocyte (CTL) activity was reduced after treatment with 4,000 J/m2, but a significant level of cytotoxicity was still maintained. Natural killer cell cytolytic activity was not affected by doses up to 4,000 J/m2. At 4,000 J+m2 there was a 10% survival of colony-forming units-granulocyte-macrophage; a 1% and 4% survival of day-8 and day-12 colony-forming units-spleen, respectively; and 11% survival of marrow repopulating ability cells. Up to 25% of late cobblestone area forming cells (4 to 5 weeks), reflecting the more immature hematopoietic stem cells, were preserved in bone marrow treated with 4,000 J/m2, indicating that early stem cells are less sensitive to UVB damage than are more committed progenitor cells. Thus, a potential therapeutic window was established at approximately 4,000 J/m2 using this light source, whereby the potentially GVHD-inducing T cells were suppressed, but a sufficient proportion of the cells responsible for engraftment was maintained.

Efficient and Selectable Production of Reactive Species Using a Nanosecond Pulsed Discharge in Gas Bubbles in Liquid

A plasma gas bubble-in-liquid method for high production of selectable reactive species using a nanosecond pulse generator has been developed. The gas of choice is fed through a hollow needle in a point-to-plate bubble discharge, enabling improved selection of reactive species. The increased interface reactions, between the gas-plasma and water through bubbles, give higher productivity. H₂O₂ was the predominant species produced using Ar plasma, while predominantly  and NO₂ were generated using air plasma, in good agreement with the observed emission spectra. This method has nearly 100% selectivity for H₂O₂, with seven times higher production, and 92% selectivity for , with nearly twice the production, compared with a plasma above the water.