Multiwavelength Observations of EXO 0748-676. II. Emission-Line Behavior

We present optical and ultraviolet spectra, light curves, and Doppler tomograms of the low-mass X-ray binary EXO 0748-676. Using an extensive set of 15 emission-line tomograms, we show that, along with the usual emission from the stream and ``hot spot,'' there is extended nonaxisymmetric emission from the disk rim. Some of the emission and Hα and Hβ absorption features lend weight to the hypothesis that part of the stream overflows the disk rim and forms a two phase medium. The data are consistent with a 1.35 Msolar neutron star with a main-sequence companion and hence a mass ratio q~0.34.

High-speed Keck spectroscopy of flares and oscillations in AE Aquarii

Using high-time-resolution (72 ms) spectroscopy of AE Aqr obtained with LRIS on Keck II we have determined the spectrum and spectral evolution of a small flare. Continuum and integrated line fluxes in the flare spectrum are measured, and the evolution of the flare is parametrized for future comparison with detailed models of the flares. We find that the velocities of the flaring components are consistent with those previously reported for AE Aqr by Welsh, Horne & Gomer and Horne. The characteristics of the 33-s oscillations are investigated: we derive the oscillation amplitude spectrum, and from that determine the spectrum of the heated regions on the rotating white dwarf. Blackbody fits to the major and minor pulse spectra and an analysis of the emission-line oscillation properties highlight the shortfalls in the simple hotspot model for the oscillations.

Synthesis, crystal structure, and catecholase activity of three trinuclear heterometallic NiII2-MnII complexes derived from a salen-type Schiff base ligand

Three new trinuclear heterometallic nickel(II)manganese(II) complexes, [(NiL)2Mn(NCS)2] (1), [(NiL)2Mn(NCO)2] (2), and [{NiL(EtOH)}2Mn(NO2)2]center dot 2EtOH (3), have been synthesized by using [NiL] as the so-called ligand complex [where H2L = N,N'-bis(salicylidene)-1,3-propanediamine] and have been structurally characterized. Crystal structure analyses revealed that complexes 1 and 2 are angular trinuclear species, in which two terminal four-coordinate square planar [NiL] moieties are coordinated to a central MnII through double phenoxido bridges. The MnII is in a six-coordinate distorted octahedral environment that is bonded additionally to two mutually cis nitrogen atoms of terminal thiocyanate (in 1) and cyanate (in 2). In complex 3, in addition to the double phenoxo bridge, the two terminal NiII ions are linked to the central MnII by means of a nitrite bridge (1?N:2?O) that, together with a coordinated ethanol molecule, gives rise to an octahedral environment around the NiII ions and consequently the structure becomes linear. Catecholase activity of these three complexes was examined by using 3,5-di-tert-butylcatechol (3,5-DTBC) as the substrate. All three complexes mimic catecholase activity and the rate of catechol oxidation follows saturation kinetics with respect to the substrate and first-order kinetics with respect to the catalyst. The EPR spectra of the complexes exhibit characteristic six line spectra, which indicate the presence of high-spin octahedral MnII species in solution state. The ESI-MS positive spectrum of 1 in the presence of 3,5-DTBC has been recorded to investigate possible complexsubstrate intermediates.

Quantitative analysis of remote gas temperatures and concentrations from their infrared emission spectra

Techniques for obtaining quantitative values of the temperatures and concentrations of remote hot gaseous effluents from their measured passive emission spectra have been examined in laboratory experiments and on field trials. These emission spectra were obtained using an adapted FTIR spectrometer with 0.25 cm-1 spectral resolution. The CO2 and H2O vapour content in the plume from a 55 m smoke stack and the temperature of these gases were obtained by comparing the measured emission spectra with those modelled using the HITRAN atmospheric transmission database. The spatial distributions of CO2, CO and unburnt CH4 in a laboratory methane flame were reconstructed tomographically using a matrix inversion technique.

Remote gas detection and quantitative analysis from infrared emission spectra obtained by Fourier transform infrared spectroscopy

Techniques for obtaining quantitative values of the temperatures and concentrations of remote hot gaseous effluents from their measured passive emission spectra have been examined in laboratory experiments. The high sensitivity of the spectrometer in the vicinity of the 2397 cm-1 band head region of CO2 has allowed the gas temperature to be calculated from the relative intensity of the observed rotational lines. The spatial distribution of the CO2 in a methane flame has been reconstructed tomographically using a matrix inversion technique. The spectrometer has been calibrated against a black body source at different temperatures and a self absorption correction has been applied to the data avoiding the need to measure the transmission directly. Reconstruction artifacts have been reduced by applying a smoothing routine to the inversion matrix.

Rotational spectra induced by vibrations

Mizushima and Venkateswarlu showed in 1953 that certain molecules have the property that excited vibrational states may possess rotational spectra even when the rotational spectrum of the ground vibrational state is forbidden by symmetry. We call such a spectrum a vibrationally induced rotational spectrum, and have made a systematic examination of the point groups which permit such behaviour. We also give formulae for the approximate line frequencies and intensities in these spectra, and discuss some of the problems involved in observing them. The spectra can only arise from degenerate vibrational states, and are of three possible types: i) symmetric top perpendicular spectra, shown by molecules belonging to the point groups Dnh, Dn and Cnh, where n is odd; (ii) symmetric top parallel spectra, shown by molecules belonging to Dnd and S2n, where n is even; and (iii) spherical top spectra, shown by molecules belonging to T or Td. Excited vibrational states of polar molecules of point groups Cnv or Cn, where n is odd, may also possess vibrationally induced perpendicular components of type (i), in addition to their ordinary parallel spectra. In addition to the above limitations on the point groups there are, in general, limitations on the symmetry species of the degenerate vibrational states.

Vibration-rotation spectra of nitrous acid, HONO

High-resolution Fourier-transform infrared spectra have been recorded and analyzed for the nu4, nu5, and nu6 fundamental bands of trans-HONO, and for the nu4 fundamental of cis-HONO. The spectral resolution was better than 0.01/cm, and the rotational structure has been analyzed to give improved ground-state and excited-state rotational constants, with a standard deviation of the fit to the observed line positions of around 0.0006/cm. Two Coriolis interactions have been analyzed between the nu5 and nu6 bands of trans-HONO.

Theoretical rovibrational line intensities in the electronic ground state of ozone

First-principles calculations of absolute line intensities and rovibrational energies of ozone (O-16(3)) are reported using potential energy and electric dipole moment functions calculated by the internally contracted MRCI approach. The rovibrational energies and eigenfunctions (up to about 8500 cm(-1) and J = 64) were obtained variationally with an exact Hamiltonian in internal valence coordinates. More than 4.8 x 10(6) electric dipole transition matrix elements were calculated for the absolute rovibrational line intensities. They are compared with the values of the HITRAN database. The purely rotational absolute line intensities in the (000) state and the rovibrational intensities for the (001)-(000) band agree to within about 0.3 to 1% for the (0 10)-(000) band to within about 3 to 4%. Excellent agreement with experiment is also achieved for low-lying overtone and combination bands. Inconsistencies are found for the (100)-(000) band overlapping with the antisymmetric stretching fundamental and also for the (002)-(000) antisymmetric stretching overtone. The generated dipole moment function can be used for predicting the absorption intensities in any of the heavier isotopomers, hot bands or the rates of spontaneous emission.

A novel heteroditopic terpyridine-pincer ligand as building block for mono- and heterometallic Pd(II) and Ru(II) complexes

A palladium-catalyzed Stille coupling reaction was employed as a versatile method for the synthesis of a novel terpyridine-pincer (3, TPBr) bridging ligand, 4'-{4-BrC6H2(CH2NMe2)(2)-3,5}-2,2':6',2 ''-terpyridine. Mononuclear species [PdX(TP)] (X = Br, Cl), [Ru(TPBr)(tpy)](PF6)(2), and [Ru(TPBr)(2)](PF6)(2), synthesized by selective metalation of the NCNBr-pincer moiety or complexation of the terpyridine of the bifunctional ligand TPBr, were used as building blocks for the preparation of heterodi- and trimetallic complexes [Ru(TPPdCl)(tpy)](PF6)(2) (7) and [Ru(TPPdCl)(2)]-(PF6)(2) (8). The molecular structures in the solid state of [PdBr(TP)] (4a) and [Ru(TPBr)(2)](PF6)(2) (6) have been determined by single-crystal X-ray analysis. Electrochemical behavior and photophysical properties of the mono-and heterometallic complexes are described. All the above di- and trimetallic Ru complexes exhibit absorption bands attributable to (MLCT)-M-1 (Ru -> tpy) transitions. For the heteroleptic complexes, the transitions involving the unsubstituted tpy ligand are at a lower energy than the tpy moiety of the TPBr ligand. The absorption bands observed in the electronic spectra for TPBr and [PdCl(TP)] have been assigned with the aid of TD-DFT calculations. All complexes display weak emission both at room temperature and in a butyronitrile glass at 77 K. The considerable red shift of the emission maxima relative to the signal of the reference compound [Ru(tpy)(2)](2+) indicates stabilization of the luminescent (MLCT)-M-3 state. For the mono- and heterometallic complexes, electrochemical and spectroscopic studies (electronic absorption and emission spectra and luminescence lifetimes recorded at room temperature and 77 K in nitrile solvents), together with the information gained from IR spectroelectrochemical studies of the dimetallic complex [Ru(TPPdSCN)(tpy)](PF6)(2), are indicative of charge redistribution through the bridging ligand TPBr. The results are in line with a weak coupling between the {Ru(tpy)(2)} chromophoric unit and the (non)metalated NCN-pincer moiety.

Syntheses, x-ray structures, photochemistry, redox properties, and DFT calculations of interconvertible fac- and mer-[Mn(SPS)(CO)3] isomers containing a flexible SPS-based pincer ligand

The lithium salt of the anionic SPS pincer ligand composed of a central hypervalent lambda(4)-phosphinine ring bearing two ortho-positioned diphenylphosphine sulfide side arms reacts with [Mn(CO)(5)Br] to give fac-[Mn(SPS)(CO)(3)], This isomer can be converted photochemicaily to mer-[Mn(SPS)(CO)(3)], with a very high quantum yield (0.80 +/- 0.05). The thermal backreaction is slow (taking ca. 8 h at room temperature), in contrast to rapid electrodecatalyzed mer-to-fac isomerization triggered by electrochemical reduction of mer-[Mn(SPS)(CO)(3)]. Both geometric isomers of [Mn(SPS)(CO)(3)] have been characterized by X-ray crystallography. Both isomers show luminescence from a low-lying (IL)-I-3 (SPS-based) excited state. The light emission of fac-[Mn(SPS)(CO)(3)] is largely quenched by the efficient photoisomerization occurring probably from a low-lying Mn-CO dissociative excited state. Density functional theory (DFT) and time-dependent DFT calculations describe the highest occupied molecular orbital (HOMO) and lowest unoccupied molecular orbital (LUMO) of fac- and mer-[Mn(CO)(3)(SPS)] as ligand-centered orbitals, largely localized on the phosphinine ring of the SPS pincer ligand. In line with the ligand nature of its frontier orbitals, fac-[Mn(SPS)(CO)(3)] is electrochemically reversibly oxidized and reduced to the corresponding radical cation and anion, respectively. The spectroscopic (electron paramagnetic resonance, IR, and UV-vis) characterization of the radical species provides other evidence for the localization of the redox steps on the SIPS ligand. The smaller HOMO-LUMO energy difference in the case of mer-[Mn(CO)(3)(SPS)], reflected in the electronic absorption and emission spectra, corresponds with its lower oxidation potential compared to that of the fac isomer. The thermodynamic instability of mer-[Mn(CO)(3)(SPS)], confirmed by the DFT calculations, increases upon one-electron reduction and oxidation of the complex.

Outgoing longwave radiation due to directly transmitted surface emission

A frequently used diagram summarizing the annual- and global-mean energy budget of the earth and atmosphere indicates that the irradiance reaching the top of the atmosphere from the surface, through the midinfrared atmospheric window, is 40 W m−2; this can be compared to the total outgoing longwave radiation (OLR) of about 235 W m−2. The value of 40 W m−2 was estimated in an ad hoc manner. A more detailed calculation of this component, termed here the surface transmitted irradiance (STI), is presented, using a line-by-line radiation code and 3D climatologies of temperature, humidity, cloudiness, etc. No assumption is made as to the wavelengths at which radiation from the surface can reach the top of the atmosphere. The role of the water vapor continuum is highlighted. In clear skies, if the continuum is excluded, the global- and annual-mean STI is calculated to be about 100 W m−2 with a broad maximum throughout the tropics and subtropics. When the continuum is included, the clear-sky STI is reduced to 66 W m−2, with a distinctly different geographic distribution, with a minimum in the tropics and local peaks over subtropical deserts. The inclusion of clouds reduces the STI to about 22 W m−2. The actual value is likely somewhat smaller due to processes neglected here, and an STI value of 20 W m−2 (with an estimated uncertainty of about ±20%) is suggested to be much more realistic than the previous estimate of 40 W m−2. This indicates that less than one-tenth of the OLR originates directly from the surface.

Methane in the atmosphere of the transiting hot Neptune GJ436b?

We present an analysis of seven primary transit observations of the hot Neptune GJ436b at 3.6, 4.5, and 8 μm obtained with the Infrared Array Camera on the Spitzer Space Telescope. After correcting for systematic effects, we fitted the light curves using the Markov Chain Monte Carlo technique. Combining these new data with the EPOXI, Hubble Space Telescope, and ground-based V, I, H, and Ks published observations, the range 0.5-10 μm can be covered. Due to the low level of activity of GJ436, the effect of starspots on the combination of transits at different epochs is negligible at the accuracy of the data set. Representative climate models were calculated by using a three-dimensional, pseudospectral general circulation model with idealized thermal forcing. Simulated transit spectra of GJ436b were generated using line-by-line radiative transfer models including the opacities of the molecular species expected to be present in such a planetary atmosphere. A new, ab-initio-calculated, line list for hot ammonia has been used for the first time. The photometric data observed at multiple wavelengths can be interpreted with methane being the dominant absorption after molecular hydrogen, possibly with minor contributions from ammonia, water, and other molecules. No clear evidence of carbon monoxide and carbon dioxide is found from transit photometry. We discuss this result in the light of a recent paper where photochemical disequilibrium is hypothesized to interpret secondary transit photometric data. We show that the emission photometric data are not incompatible with the presence of abundant methane, but further spectroscopic data are desirable to confirm this scenario.

IMF control of cusp proton emission intensity and dayside convection: implications for component and anti-parallel reconnection

We study a brightening of the Lyman-alpha emission in the cusp which occurred in response to a short-lived southward turning of the interplanetary magnetic field (IMF) during a period of strongly enhanced solar wind plasma concentration. The cusp proton emission is detected using the SI-12 channel of the FUV imager on the IMAGE spacecraft. Analysis of the IMF observations recorded by the ACE and Wind spacecraft reveals that the assumption of a constant propagation lag from the upstream spacecraft to the Earth is not adequate for these high time-resolution studies. The variations of the southward IMF component observed by ACE and Wind allow for the calculation of the ACE-to-Earth lag as a function of time. Application of the derived propagation delays reveals that the intensity of the cusp emission varied systematically with the IMF clock angle, the relationship being particularly striking when the intensity is normalised to allow for the variation in the upstream solar wind proton concentration. The latitude of the cusp migrated equatorward while the lagged IMF pointed southward, confirming the lag calculation and indicating ongoing magnetopause reconnection. Dayside convection, as monitored by the SuperDARN network of radars, responded rapidly to the IMF changes but lagged behind the cusp proton emission response: this is shown to be as predicted by the model of flow excitation by Cowley and Lockwood (1992). We use the numerical cusp ion precipitation model of Lockwood and Davis (1996), along with modelled Lyman-_ emission efficiency and the SI-12 instrument response, to investigate the effect of the sheath field clock angle on the acceleration of ions on crossing the dayside magnetopause. This modelling reveals that the emission commences on each reconnected field line 2–2.5min after it is opened and peaks 3–5 min after it is opened. We discuss how comparison of the Lyman-alpha intensities with oxygen emissions observed simultaneously by the SI-13 channel of the FUV instrument offers an opportunity to test whether or not the clock angle dependence is consistent with the “component” or the “anti-parallel” reconnection hypothesis.

Coherent EISCAT Svalbard Radar spectra from the dayside cusp/cleft and their implications for transient field-aligned currents

Naturally enhanced incoherent scatter spectra from the vicinity of the dayside cusp/cleft, interpreted as being due to plasma turbulence driven by short bursts of intense field-aligned current, are compared with high-resolution narrow-angle auroral images and meridian scanning photometer data. Enhanced spectra have been observed on many occasions in association with nightside aurora, but there has been only one report of such spectra seen in the cusp/cleft region. Narrow-angle images show considerable change in the aurora on timescales shorter than the 10-s radar integration period, which could explain spectra observed with both ion lines simultaneously enhanced. Enhanced radar spectra are generally seen inside or beside regions of 630-nm auroral emission, indicative of sharp F region conductivity gradients, but there appears also to be a correlation with dynamic, small-scale auroral forms of order 100 m and less in width.

Location and characteristics of the reconnection X line deduced from low-altitude satellite and ground-based observations: 1. Theory

A method for estimating both the Alfvén speed and the field-aligned flow of the magnetosheath at the magnetopause reconnection site is presented. The method employs low-altitude cusp ion observations and requires the identification of a feature in the cusp ion spectra near the low-energy cutoff which will often be present for a low-latitude dayside reconnection site. The appearance of these features in data of limited temporal, energy, and pitch angle resolution is illustrated by using model calculations of cusp ion distribution functions. These are based on the theory of ion acceleration at the dayside magnetopause and allow for the effects on the spectrum of flight times of ions precipitating down newly opened field lines. In addition, the variation of the reconnection rate can be evaluated, and comparison with ground-based observations of the corresponding sequence of transient events allows the field-aligned distance from the ionosphere to the reconnection site to be estimated.