Effects of rotation in the laser-pulse photoassociation in a thermal gas of atoms

Photoassociation is a possible route for the formation of chemical bonds. In this process, the binding of colliding atoms can be induced by means of a laser field. Photoassociation has been studied in the ultracold regime and also with temperatures well above millikelvins in the thermal energy domain, which is a situation commonly encountered in the laboratory. A photoassociation mechanism can be envisioned based on the use of infrared pulses to drive a transition from free colliding atoms on the electronic ground state to form a molecule directly on that state. This work takes a step in this direction, investigating the laser-pulse-driven formation of heteronuclear diatomic molecules in a thermal gas of atoms including rotational effects. Based on the assumption of full system controllability, the maximum possible photoassociation yield is deduced. The photoassociation probability is calculated as a function of the laser parameters for different temperatures. Additionally, the photoassociation yield induced by subpicosecond pulses of a priori fixed shape is compared to the maximum possible yield.

Genetic model of the hydrate system in the fine grain sediments in the northern continental slope of South China Sea

Gas hydrate samples were obtained firstly in China by drilling on the northern margin of South China Sea (SCS). To understand the formation mechanism of this unique accumulation system, this paper discusses the factors controlling the formation of the system by accurate geophysical interpretation and geological analysis, based on the high precision 2-D and 3-D multichannel seismic data in the drilling area. There are three key factors controlling the accumulation of the gas hydrate system in fine grain sediment: (1) large volume of fluid bearing methane gas Joins the formation of gas hydrate. Active fluid flow in the northern South China Sea makes both thermal gas and/or biogenic gas migrate into shallow strata and form hydrate in the gas hydrate stability zone (GHSZ). The fluid flow includes mud diapir and gas chimney structure. They are commonly characterized by positive topographic relief, acoustic turbidity and push-down, and low reflection intensity on seismic profiles. The gas chimneys can reach to GHSZ, which favors the development of BSRs. It means that the active fluid flow has a close relationship with the formation and accumulation of gas hydrate. (2) The episodic process of fracture plays an important role in the generation of gas hydrate. It may provide the passage along which thermogenic or biogenic gas migrated into gas hydrate stability zone (GHSZ) upward. And it increases the pore space for the growth of hydrate crystal. (3) Submarine landslide induced the anomalous overpressure activity and development of fracture in the GHSZ. The formation model of high concentration gas hydrate in the drilling sea area was proposed on the basis of above analysis.

GIANT LOBES OF CENTAURUS A RADIO GALAXY OBSERVED WITH THE SUZAKU X-RAY SATELLITE

We report on Suzaku observations of selected regions within the southern giant lobe of the radio galaxy Centaurus A. In our analysis we focus on distinct X-ray features detected with the X-ray Imaging Spectrometer within the range 0.5-10 keV, some of which are likely associated with fine structure of the lobe revealed by recent high-quality radio intensity and polarization maps. With the available photon statistics, we find that the spectral properties of the detected X-ray features are equally consistent with thermal emission from hot gas with temperatures kT > 1 keV, or with a power-law radiation continuum characterized by photon indices Gamma similar to 2.0 +/- 0.5. However, the plasma parameters implied by these different models favor a synchrotron origin for the analyzed X-ray spots, indicating that a very efficient acceleration of electrons up to greater than or similar to 10 TeV energies is taking place within the giant structure of Centaurus A, albeit only in isolated and compact regions associated with extended and highly polarized radio filaments. We also present a detailed analysis of the diffuse X-ray emission filling the whole field of view of the instrument, resulting in a tentative detection of a soft excess component best fitted by a thermal model with a temperature of kT similar to 0.5 keV. The exact origin of the observed excess remains uncertain, although energetic considerations point to thermal gas filling the bulk of the volume of the lobe and mixed with the non-thermal plasma, rather than to the alternative scenario involving a condensation of the hot intergalactic medium around the edges of the expanding radio structure. If correct, this would be the first detection of the thermal content of the extended lobes of a radio galaxy in X-rays. The corresponding number density of the thermal gas in such a case is n(g) similar to 10(-4) cm(-3), while its pressure appears to be in almost exact equipartition with the volume-averaged non-thermal pressure provided by the radio-emitting electrons and the lobes' magnetic field. A prominent large-scale fluctuation of the Galactic foreground emission, resulting in excess foreground X-ray emission aligned with the lobe, cannot be ruled out. Although tentative, our findings potentially imply that the structure of the extended lobes in active galaxies is likely to be highly inhomogeneous and non-uniform, with magnetic reconnection and turbulent acceleration processes continuously converting magnetic energy to internal energy of the plasma particles, leading to possibly significant spatial and temporal variations in the plasma beta parameter around the volume-averaged equilibrium condition beta similar to 1.

Hierarchical energy management system for multi-source multi-product microgrids

This paper proposes a hierarchical energy management system for multi-source multi-product (MSMP) microgrids. Traditional energy hub based scheduling method is combined with a hierarchical control structure to incorporate transient characteristics of natural gas flow and dynamics of energy converters in microgrids. The hierarchical EMS includes a supervisory control layer, an optimizing control layer, and an execution control layer. In order to efficiently accommodate the systems multi time-scale characteristics, the optimizing control layer is decomposed into three sub-layers: slow, medium and fast. Thermal, gas and electrical management systems are integrated into the slow, medium, and fast control layer, respectively. Compared with wind energy, solar energy is easier to integrate and more suitable for the microgrid environment, therefore, potential impacts of the hierarchical EMS on MSMP microgrids is investigated based on a building energy system integrating photovoltaic and microturbines. Numerical studies indicate that by using a hierarchical EMS, MSMP microgrids can be economically operated. Also, interactions among thermal, gas, and electrical system can be effectively managed.

Radio relics and magnetic fields in galaxy clusters

Radio relics are diffuse synchrotron sources generally located in the peripheries of galaxy clusters in merging state. According to the current leading scenario, relics trace gigantic cosmological shock waves that cross the intra-cluster medium where particle acceleration occurs. The relic/shock connection is supported by several observational facts, including the spatial coincidence between relics and shocks found in the X-rays. Under the assumptions that particles are accelerated at the shock front and are subsequently deposited and then age downstream of the shock, Markevitch et al. (2005) proposed a method to constrain the magnetic field strength in radio relics. Measuring the thickness of radio relics at different frequencies allows to derive combined constraints on the velocity of the downstream flow and on the magnetic field, which in turns determines particle aging. We elaborate this idea to infer first constraints on magnetic fields in cluster outskirts. We consider three models of particle aging and develop a geometric model to take into account the contribution to the relic transverse size due to the projection of the shock-surface on the plane of the sky. We selected three well studied radio relics in the clusters A 521, CIZA J2242.8+5301 and 1RXS J0603.3+4214. These relics have been chosen primarily because they are almost seen edge-on and because the Mach number of the shock that is associated with these relics is measured by X-ray observations, thus allowing to break the degeneracy between magnetic field and downstream velocity in the method. For the first two clusters, our method is consistent with a pure radiative aging model allowing us to derive constraints on the relics magnetic field strength. In the case of 1RXS J0603.3+4214 we find that particle life-times are consistent with a pure radiative aging model under some conditions, however we also collect evidences for downstream particle re-acceleration in the relic W-region and for a magnetic field decaying downstream in its E-region. Our estimates of the magnetic field strength in the relics in A 521 and CIZA J2242.8+5301 provide unique information on the field properties in cluster outskirts. The constraints derived for these relics, together with the lower limits to the magnetic field that we derived from the lack of inverse Compton X-ray emission from the sources, have been combined with the constraints from Faraday rotation studies of the Coma cluster. Overall results suggest that the spatial profile of the magnetic field energy density is broader than that of the thermal gas, implying that the ε_th /ε_B ratio decreases with cluster radius. Alternatively, radio relics could trace dynamically active regions where the magnetic field strength is biased high with respect to the average value in the cluster volume.

Ionisation and discharge in cloud-forming atmospheres of brown dwarfs and extrasolar planets

Brown dwarfs and giant gas extrasolar planets have cold atmospheres with rich chemical compositions from which mineral cloud particles form. Their properties, like particle sizes and material composition, vary with height, and the mineral cloud particles are charged due to triboelectric processes in such dynamic atmospheres. The dynamics of the atmospheric gas is driven by the irradiating host star and/or by the rotation of the objects that changes during its lifetime. Thermal gas ionisation in these ultra-cool but dense atmospheres allows electrostatic interactions and magnetic coupling of a substantial atmosphere volume. Combined with a strong magnetic field , a chromosphere and aurorae might form as suggested by radio and x-ray observations of brown dwarfs. Non-equilibrium processes like cosmic ray ionisation and discharge processes in clouds will increase the local pool of free electrons in the gas. Cosmic rays and lighting discharges also alter the composition of the local atmospheric gas such that tracer molecules might be identified. Cosmic rays affect the atmosphere through air showers in a certain volume which was modelled with a 3D Monte Carlo radiative transfer code to be able to visualise their spacial extent. Given a certain degree of thermal ionisation of the atmospheric gas, we suggest that electron attachment to charge mineral cloud particles is too inefficient to cause an electrostatic disruption of the cloud particles. Cloud particles will therefore not be destroyed by Coulomb explosion for the local temperature in the collisional dominated brown dwarf and giant gas planet atmospheres. However, the cloud particles are destroyed electrostatically in regions with strong gas ionisation. The potential size of such cloud holes would, however, be too small and might occur too far inside the cloud to mimic the effect of, e.g. magnetic field induced star spots.

Insight into the thermal decomposition of kaolinite intercalated with potassium acetate : an evolved gas analysis

The thermal decomposition process of kaolinite–potassium acetate intercalation complex has been studied using simultaneous thermogravimetry coupled with Fourier-transform infrared spectroscopy and mass spectrometry (TG-FTIR-MS). The results showed that the thermal decomposition of the complex took place in four temperature ranges, namely 50–100, 260–320, 320–550, and 650–780 °C. The maximal mass losses rate for the thermal decomposition of the kaolinite–potassium acetate intercalation complex was observed at 81, 296, 378, 411, 486, and 733 °C, which was attributed to (a) loss of the adsorbed water, (b) thermal decomposition of surface-adsorbed potassium acetate (KAc), (c) the loss of the water coordinated to potassium acetate in the intercalated kaolinite, (d) the thermal decomposition of intercalated KAc in the interlayer of kaolinite and the removal of inner surface hydroxyls, (e) the loss of the inner hydroxyls, and (f) the thermal decomposition of carbonate derived from the decomposition of KAc. The thermal decomposition of intercalated potassium acetate started in the range 320–550 °C accompanied by the release of water, acetone, carbon dioxide, and acetic acid. The identification of pyrolysis fragment ions provided insight into the thermal decomposition mechanism. The results showed that the main decomposition fragment ions of the kaolinite–KAc intercalation complex were water, acetone, carbon dioxide, and acetic acid. TG-FTIR-MS was demonstrated to be a powerful tool for the investigation of kaolinite intercalation complexes. It delivers a detailed insight into the thermal decomposition processes of the kaolinite intercalation complexes characterized by mass loss and the evolved gases.

Internal nitride formation during gas-phase thermal nitridation of titanium

Titanium nitride surface layers were prepared by gas-phase thermal nitridation of pure titanium in an ammonia atmosphere at 1373 K for different times. In addition to the surface nitride layer, nitride/hydride formation was observed in the bulk of the specimen. The cross-section of the specimen was characterized by various techniques such as optical microscopy, scanning electron microscopy, energy dispersive X-ray spectroscopy, secondary ion mass spectrometry and nanomechanical testing, and the mechanism of formation of these phases is discussed.

Nonlinear intrinsic instability of solid propellant combustion including gas-phase thermal inertia

The problem of homogeneous solid propellant combustion instability is studied with a one-dimensional flame model, including the effects of gas-phase thermal inertia and nonlinearity. Computational results presented in this paper show nonlinear instabilities inherent in the equations, due to which periodic burning is found even under steady ambient conditions such as pressure. The stability boundary is obtained in terms of Denison-Baum parameters. It is found that inclusion of gas-phase thermal inertia stabilizes the combustion. Also, the effect of a distributed heat release in the gas phase, compared to the flame sheet model, is to destabilize the burning. Direct calculations for finite amplitude pressure disturbances show that two distinct resonant modes exist, the first one near the natural frequency as obtained from intrinsic instability analysis and a second mode occurring at a much higher driving frequency. It is found that er rn in the low frequency region, the response of the propellant is significantly affected by the specific type of gas-phase chemical heat-release model employed. Examination of frequency response function reveals that the role of gas-phase thermal inertia is to stabilize the burning near the first resonant mode. Calculations made for different amplitudes of driving pressure show that the mean burning rate decreases with increasing amplitude. Also, with an increase in the driving amplitude, higher harmonics are generated in the burning rate.

Design and fabrication of an automated thermal desorption gas-solid reaction system: Oxidation of ammonia and methanol over YBa2Cu3O7−δ(123) oxide systems

A fully automated, versatile Temperature Programmed Desorption (TDP), Temperature Programmed Reaction (TPR) and Evolved Gas Analysis (EGA) system has been designed and fabricated. The system consists of a micro-reactor which can be evacuated to 10−6 torr and can be heated from 30 to 750°C at a rate of 5 to 30°C per minute. The gas evolved from the reactor is analysed by a quadrupole mass spectrometer (1–300 amu). Data on each of the mass scans and the temperature at a given time are acquired by a PC/AT system to generate thermograms. The functioning of the system is exemplified by the temperature programmed desorption (TPD) of oxygen from YBa2Cu3−xCoxO7 ± δ, catalytic ammonia oxidation to NO over YBa2Cu3O7−δ and anaerobic oxidation of methanol to CO2, CO and H2O over YBa2Cu3O7−δ (Y123) and PrBa2Cu3O7−δ (Pr123) systems.

Thermal degradation products of poly(styrenesulfides) investigated by direct pyrolysis�mass spectrometry and flash pyrolysis�gas chromatography/mass spectrometry

The thermal degradation products of two sulfur polymers, poly(styrenedisulfide) (PSD) and poly(styrenetetrasulfide) (PST), were investigated in parallel by direct pyrolysis-mass spectrometry (DPMS) and by flash pyrolysis-GC/MS (Py-GC/MS). The time-scale of the two pyrolysis techniques is quite different, and therefore they were able to detect significantly different products in the pyrolysis of PSD and PST because of the thermal lability of sulfur-containing compounds. However, the results obtained are not contradictory, and satisfactory mechanisms for the thermal degradation of PSD and PST have been derived from the overall evidence available. Pyrolysis compounds containing sulfur, styrene, and a number of cyclic styrene sulfides and diphenyldithianes have been observed by DPMS. However, in flash pyrolysis-GC/MS, styrene, sulfur, only one cyclic styrene sulfide, and two isomers of diphenylthiophene have been detected. These thiophene derivatives were indeed absent among the compounds obtained by DPMS because they were the terminal (most thermally stable) species arising from further decomposition of the cyclic styrene sulfides formed in the primary thermal degradation processes of PSD and PST.

Thermal degradation processes in polysulfide copolymers investigated by direct pyrolysis mass spectrometry and flash pyrolysis-gas chromatography/mass spectrometry

This is the first report on the analysis of random block polysulfide copolymers containing different amounts of repeating units in the copolymer backbone, which has been studied by direct pyrolysis mass spectrometry (DPMS) and by pyrolysis-gas chromatography/mass spectrometry (Py-GC/MS). The homopolymers such as poly(ethylene sulfide) (PES), poly(styrene sulfide) (PSS), and two random copolymers, viz., poly(ethylene sulfide(x)-co-styrene sulfide(y)) [copolymer I (x = y = 0.5) and copolymer II (x = 0.74, y = 0.26)] were investigated by both DPMS and Py-GC/MS (except copolymer II) techniques. In the case of copolymer I, the thermal degradation products of SE1, SE2, S-2, and S2E (S = styrene sulfide, E = ethylene sulfide) were detected in DPMS, whereas the formation of SE1 and SE2 were observed by Py-GC/MS technique. However, for copolymer II, SE3 was also found along with SE1, SE2, S-2, and S2E in DPMS. The formation of additional product (SE3) observed in copolymer II could be due to an increase in the block length formed during copolymerization. Further, a comparative study on thermal degradation of PES, poly(ethylene disulfide) (PEDS), and poly(ethylene tetrasulfide) (PETS) were investigated by Py-GC/MS. The pyrolysis products detected by both DPMS and Py-GC/MS indicates that the thermal decomposition of these polymers yield cyclic sulfides through an intramolecular exchange or by backbiting processes. The linear products with thiol and vinyl groups were also observed by Py-GC/MS along with the cyclic products via carbon hydrogen transfer reaction.

Information content of molecular graph and prediction of gas phase thermal entropy of organic compounds

Entropy is a fundamental thermodynamic property that has attracted a wide attention across domains, including chemistry. Inference of entropy of chemical compounds using various approaches has been a widely studied topic. However, many aspects of entropy in chemical compounds remain unexplained. In the present work, we propose two new information-theoretical molecular descriptors for the prediction of gas phase thermal entropy of organic compounds. The descriptors reflect the bulk and size of the compounds as well as the gross topological symmetry in their structures, all of which are believed to determine entropy. A high correlation () between the entropy values and our information-theoretical indices have been found and the predicted entropy values, obtained from the corresponding statistically significant regression model, have been found to be within acceptable approximation. We provide additional mathematical result in the form of a theorem and proof that might further help in assessing changes in gas phase thermal entropy values with the changes in molecular structures. The proposed information-theoretical molecular descriptors, regression model and the mathematical result are expected to augment predictions of gas phase thermal entropy for a large number of chemical compounds.