Local luminous infrared galaxies. I. Spatially resolved observations with the Spitzer infrared spectrograph

We present results from the Spitzer Infrared Spectrograph spectral mapping observations of 15 local luminous infrared galaxies (LIRGs). In this paper, we investigate the spatial variations of the mid-IR emission which includes fine structure lines, molecular hydrogen lines, polycyclic aromatic features (PAHs), continuum emission, and the 9.7 μm silicate feature. We also compare the nuclear and integrated spectra. We find that the star formation takes place in extended regions (several kpc) as probed by the PAH emission, as well as the [Ne II]12.81 μm and [Ne III]15.56 μm emissions. The behavior of the integrated PAH emission and 9.7 μm silicate feature is similar to that of local starburst galaxies. We also find that the minima of the [Ne III]15.56 μm/[Ne II]12.81 μm ratio tends to be located at the nuclei and its value is lower than that of H II regions in our LIRGs and nearby galaxies. It is likely that increased densities in the nuclei of LIRGs are responsible for the smaller nuclear [Ne III]15.56 μm/[Ne II]12.81 μm ratios. This includes the possibility that some of the most massive stars in the nuclei are still embedded in ultracompact H II regions. In a large fraction of our sample, the 11.3 μm PAH emission appears more extended than the dust 5.5 μm continuum emission. We find a dependency of the 11.3 μm PAH/7.7 μm PAH and [Ne II]12.81 μm/11.3 μm PAH ratios with the age of the stellar populations. Smaller and larger ratios, respectively, indicate recent star formation. The estimated warm (300 K

Research Update: Photoelectrochemical water splitting and photocatalytic hydrogen production using ferrites (MFe2O4) under visible light irradiation

The utilization of solar light for the photoelectrochemical and photocatalytic production of molecular hydrogen from water is a scientific and technical challenge. Semiconductors with suitable properties to promote solar-driven water splitting are a desideratum. A hitherto rarely investigated group of semiconductors are ferrites with the empirical formula MFe2O4 and related compounds. This contribution summarizes the published results of the experimental investigations on the photoelectrochemical and photocatalytic properties of these compounds. It will be shown that the potential of this group of compounds in regard to the production of solar hydrogen has not been fully explored yet.

Van der Waals-corrected density functional theory : benchmarking for hydrogen–nanotube and nanotube–nanotube interactions

Density functional theory (DFT) is a powerful approach to electronic structure calculations in extended systems, but suffers currently from inadequate incorporation of long-range dispersion, or Van der Waals (VdW) interactions. VdW-corrected DFT is tested for interactions involving molecular hydrogen, graphite, single-walled carbon nanotubes (SWCNTs), and SWCNT bundles. The energy correction, based on an empirical London dispersion term with a damping function at short range, allows a reasonable physisorption energy and equilibrium distance to be obtained for H2 on a model graphite surface. The VdW-corrected DFT calculation for an (8, 8) nanotube bundle reproduces accurately the experimental lattice constant. For H2 inside or outside an (8, 8) SWCNT, we find the binding energies are respectively higher and lower than that on a graphite surface, correctly predicting the well known curvature effect. We conclude that the VdW correction is a very effective method for implementing DFT calculations, allowing a reliable description of both short-range chemical bonding and long-range dispersive interactions. The method will find powerful applications in areas of SWCNT research where empirical potential functions either have not been developed, or do not capture the necessary range of both dispersion and bonding interactions.

The role of V2O5 on the dehydrogenation and hydrogenation in magnesium hydride : An ab initio study

Ab initio density functional theory calculations are performed to study the experimentally observed catalytic role of V2O5 in the recycling of hydrogen in magnesium hydride. We find that the Mg–H bond length becomes elongated when MgH2 clusters are positioned on single, two, and three coordinated oxygen sites (O1, O2, and O3) on the V2O5(001) surface. Molecular hydrogen is predicted to spontaneously form at the hole site on the V2O5(001) surface. Additionally, the activation barrier for the dissociation of hydrogen on V-doped Mg(0001) surface is 0.20 eV, which is only 1/5 of that on pure Mg(0001) surface. Our results indicate that oxygen sites on the V2O5(001)surface and the V dopant in Mg may be important facilitators for dehydrogenation and rehydrogenation, respectively. The understanding gained here will aid in the rational design and development of Mg-based hydrogen storage materials.

Cumulenic and heterocumulenic anions : potential interstellar species?

A recent theoretical investigation by Terzieva & Herbst of linear carbon chains, C-n where n greater than or equal to 6, in the interstellar medium has shown that these species can undergo efficient radiative association to form the corresponding anions. An experimental study by Barckholtz, Snow & Bierbaum of these anions has demonstrated that they do not react efficiently with molecular hydrogen, leading to the possibility of detectable abundances of cumulene-type anions in dense interstellar and circumstellar environments. Here we present a series of electronic structure calculations which examine possible anionic candidates for detection in these media, namely the anion analogues of the previously identified interstellar cumulenes CnH and Cn-1CH2 and heterocumulenes CnO (where n = 2-10). The extraordinary electron affinities calculated for these molecules suggest that efficient radiative electron attachment could occur, and the large dipole moments of these simple (generally) linear molecules point to the possibility of detection by radio astronomy.

Palladium(II) and platinum(II) complexes of beta-functionalized ethyl selenolates: Effect of substitution on synthesis, reactivity, spectroscopy, structures and thermal behavior

Sodium ethylselenolates with functional groups X (where X = -OH, -COOH, -COOMe and -COOEt) at beta-carbon were prepared in situ by reductive cleavage of corresponding diselenide with NaBH4 either in methanol or aqueous ammonia. Treatment of these selenolates with [M2Cl2(mu-Cl)(2)(PR'(3))(2)] (M = Pd or Pt; PR'(3) = PMePh2, PnPr(3)) in different stoichiometry yielded various bi- and tri-nuclear complexes. The homoleptic hexanuclear complexes [Pd(mu-SeCH2CH2X)(2)](6) (X = OH, COOH, COOEt), were obtained by reacting Na2PdCl4 with NaSeCH2CH2X. All these complexes have been fully characterized. Molecular structures of ethylselenolates containing hydroxyl and carboxylic acid groups revealed solid state associated structures through inter-molecular hydrogen bond interactions. Trinuclear complex, [Pd3Cl2(mu-SeCH2CH2COOH)(4)(PnPr(3))(2)] (3a), was disposed in a boat form unlike chair conformation observed for the corresponding methylester complex. The effect of beta-functionality in ethylselenolate ligands towards reactivity, structures and thermal properties of palladium and platinum complexes has been extensively Studied.

Interaction of metal ions with 6-oxopurine nucleotides. Part 2. X-Ray structures of ternary nickel(II) complexes with 2'-deoxyguanosine 5'-monophosphate or guanosine 5'-monophosphate

The ternary metal nucleotide complexes [Ni(en)1.3(H2O)1.4(H2O)2][Ni(5?-dGMP)2(en)0.7-(H2O)0.6(H2O)2]·7H2O (1) and [Ni(en)2(H2O)2][Ni(5?-GMP)2(H2O)4]·6H2O (2)(en = ethylenediamine, 5?-dGMP = 2?-deoxyguanosine 5?-monophosphate, 5?-GMP = guanosine 5?-monophosphate) have been prepared and their structures analyzed by X-ray diffraction methods. Both compounds crystallise in the space group C2221 with a= 8.810(1), b= 25.090(4), c= 21.084(1)Å, and Z= 4 for (1) and a= 8.730(1), b= 25.691(4), c= 21.313(5)Å, and Z= 4 for (2). The structures were deduced from the analogous CoIII complexes and refined by full-matrix least-squares methods to final R values of 0.087 and 0.131 for 1 211 and 954 reflections for (1) and (2) respectively. An interesting feature of the deoxyribonucleotide complex (1) is that en is not totally labilized from the metal centre on nucleotide co-ordination, as observed in corresponding ribonucleotide complexes. Apart from extensive intra- and inter-molecular hydrogen bonding, the structures are stabilized by significant intracomplex base�base and base�sugar interactions. The nucleotides in both complexes have an anti base, C(2?)-endo sugar pucker, and gauche�gauche conformation about the C(4?)�C(5?) bond.

Luminosity profiles of advanced mergers of galaxies using 2MASS data

A sample of 27 disturbed galaxies that show signs of interaction but have a single nucleus were selected from the Arp and the Arp-Madore catalogues. For these, the Ks band images from the Two Micron All Sky Survey (2MASS) are analysed to obtain their radial luminosity pro�les and other structural parameters. We �nd that in spite of their similar optical appearance, the sample galaxies vary in their dynamical properties, and fall into two distinct classes. The �rst class consists of galaxies which can be described by a single r1=4 law and the second class consists of galaxies that show an outer exponential disk. A few galaxies that have disturbed pro�les cannot be �t into either of the above classes. However, all the galaxies are similar in all other parameters such as the far-infrared colours, the molecular hydrogen content and the central velocity dispersion. Thus, the dynamical parameters of these sets seem to be determined by the ratio of the initial masses of the colliding galaxies. We propose that the galaxies in the �rst class result from a merger of spiral galaxies of equal masses whereas the second class of galaxies results from a merger of unequal mass galaxies. The few objects that do not fall into either category show a disturbed luminosity pro�le and a wandering centre, which is indicative of these being unrelaxed mergers. Of the 27 galaxies in our sample, 9 show elliptical-like pro�les and 13 show an outer exponential. Interestingly, Arp 224, the second oldest merger remnant of the Toomre sequence shows an exponential disk in the outer parts.

PROPENSITIES OF AMINO ACID RESIDUES IN PROTEINS FOR DIFFERENT REGIONS OF THE RAMACHANDRAN MAP

Using a dataset of 1164 crystal structures of largely non-homologous proteins defined at a resolution of 1.5 angstrom or better, we have investigated the (phi,psi) preferences of 20 residue types by considering the residues which occur in loops. Propensities of residue types to occur in the loops with (phi,psi) values in the aa region of the Ramachandran map has a poor correlation coefficient of 0.48 to the Chou-Fasman propensities of the residue types to occur in the a-helical segments. However the correlation coefficient between propensities of residues in loops to adopt beta conformations and those in beta-sheet is much higher (0.95). These observations suggest that a-helix formation is well influenced by the local amino acid sequence while intrinsic preference of residue types for beta-sheet plays a major role in the formation of beta-sheet. The main chain polar groups of residues in loops, that can affect the (phi,psi) values, can be involved in intra-molecular hydrogen bonding. Therefore we investigated further by considering subset of residues in loops with low (0 to 2) number of intra-molecular hydrogen bonds per residue involving main chain polar atoms. For this subset, the correlation coefficients between propensities for alpha-helix and alpha(R) region and between beta-sheet and beta-region are 0.26 and 0.64 respectively. This reiterates higher intrinsic tendency of beta-region favouring residues to adopt beta-sheet than alpha(R) region favouring residues to adopt alpha-helical structure.

DOES THE CHEMOTHERMAL INSTABILITY HAVE ANY ROLE IN THE FRAGMENTATION OF PRIMORDIAL GAS

The collapse of the primordial gas in the density regime similar to 10(8)-10(10) cm(-3) is controlled by the three-body H-2 formation process, in which the gas can cool faster than free-fall time-a condition proposed as the chemothermal instability. We investigate how the heating and cooling rates are affected during the rapid transformation of atomic to molecular hydrogen. With a detailed study of the heating and cooling balance in a 3D simulation of Pop III collapse, we follow the chemical and thermal evolution of the primordial gas in two dark matter minihalos. The inclusion of sink particles in modified Gadget-2 smoothed particle hydrodynamics code allows us to investigate the long-term evolution of the disk that fragments into several clumps. We find that the sum of all the cooling rates is less than the total heating rate after including the contribution from the compressional heating (pdV). The increasing cooling rate during the rapid increase of the molecular fraction is offset by the unavoidable heating due to gas contraction. We conclude that fragmentation occurs because H-2 cooling, the heating due to H-2 formation and compressional heating together set a density and temperature structure in the disk that favors fragmentation, not the chemothermal instability.

Theory of the positive column of a gas discharge

An attempt is made to provide a theoretical explanation of the effect of the positive column on the voltage-current characteristic of a glow or an arc discharge. Such theories have been developed before, and all are based on balancing the production and loss of charged particles and accounting for the energy supplied to the plasma by the applied electric field. Differences among the theories arise from the approximations and omissions made in selecting processes that affect the particle and energy balances. This work is primarily concerned with the deviation from the ambipolar description of the positive column caused by space charge, electron-ion volume recombination, and temperature inhomogeneities.

The presentation is divided into three parts, the first of which involved the derivation of the final macroscopic equations from kinetic theory. The final equations are obtained by taking the first three moments of the Boltzmann equation for each of the three species in the plasma. Although the method used and the equations obtained are not novel, the derivation is carried out in detail in order to appraise the validity of numerous approximations and to justify the use of data from other sources. The equations are applied to a molecular hydrogen discharge contained between parallel walls. The applied electric field is parallel to the walls, and the dependent variables—electron and ion flux to the walls, electron and ion densities, transverse electric field, and gas temperature—vary only in the direction perpendicular to the walls. The mathematical description is given by a sixth-order nonlinear two-point boundary value problem which contains the applied field as a parameter. The amount of neutral gas and its temperature at the walls are held fixed, and the relation between the applied field and the electron density at the center of the discharge is obtained in the process of solving the problem. This relation corresponds to that between current and voltage and is used to interpret the effect of space charge, recombination, and temperature inhomogeneities on the voltage-current characteristic of the discharge.

The complete solution of the equations is impractical both numerically and analytically, and in Part II the gas temperature is assumed uniform so as to focus on the combined effects of space charge and recombination. The terms representing these effects are treated as perturbations to equations that would otherwise describe the ambipolar situation. However, the term representing space charge is not negligible in a thin boundary layer or sheath near the walls, and consequently the perturbation problem is singular. Separate solutions must be obtained in the sheath and in the main region of the discharge, and the relation between the electron density and the applied field is not determined until these solutions are matched.

In Part III the electron and ion densities are assumed equal, and the complicated space-charge calculation is thereby replaced by the ambipolar description. Recombination and temperature inhomogeneities are both important at high values of the electron density. However, the formulation of the problem permits a comparison of the relative effects, and temperature inhomogeneities are shown to be important at lower values of the electron density than recombination. The equations are solved by a direct numerical integration and by treating the term representing temperature inhomogeneities as a perturbation.

The conclusions reached in the study are primarily concerned with the association of the relation between electron density and axial field with the voltage-current characteristic. It is known that the effect of space charge can account for the subnormal glow discharge and that the normal glow corresponds to a close approach to an ambipolar situation. The effect of temperature inhomogeneities helps explain the decreasing characteristic of the arc, and the effect of recombination is not expected to appear except at very high electron densities.

Theoretical investigation on excitation, ionization and capture in H(1s, 2s)+H(1s, 2s) collisions

Cross sections of electron- loss in H( 1s)+ H( 1s) collisions and total collisional destruction of H( 2s) in H( 1s) + H( 2s) collisions are calculated by four- body classical- trajectory Monte Carlo ( CTMC) method and compared with previous theoretical and experimental data over the energy range of 4 - 100 keV. For the former a good agreement is obtained within di. erent four- body CTMC calculations, and for the incident energy Ep > 10 keV, comparison with the experimental data shows a better agreement than the results calculated by the impact parameter approximation. For the latter, our theory predicts the correct experimental behaviour, and the discrepancies between our results and experimental ones are less than 30%. Based on the successive comparison with experiments, the cross sections for excitation to H( 2p), single- and double- ionization and H- formation in H( 2s)+ H( 2s) collisions are calculated in the energy range of 4 - 100 keV for the. rst time, and compared with those in H( 1s)+ H( 1s) and H( 1s)+ H( 2s) collisions.

Quantum-mechanical calculations of vibrationally resolved cross sections for non-dissociative charge transfer of O3+ with H-2

Charge transfer due to collisions of ground state O3+ (2s(2)2p P-2) ions with molecular hydrogen is investigated using the quantum-mechanical molecular-orbital close-coupling (MOCC) method, and electronic and vibrational state-selective cross sections along with the corresponding differential cross sections are calculated for projectile energies of 100, 500, 1000 and 5000 eV/u at the orientation angles of 25 degrees,45 degrees and 89 degrees. The adiabatic potentials and radial coupling matrix elements utilized in the QMOCC calculations were obtained with the spin-coupled valence-bond approach. The infinite order sudden approximation (IOSA) and the vibrational sudden approximation (VSA) are utilized to deal with the rotation of H-2 and the coupling between the electron and the vibration of H-2. It is found that the distribution of vibrationally resolved cross sections with the vibrational quantum number upsilon' of H-2(+) (upsilon') varies with the increment of the projectile energy; and the electronic and vibrational stateselective differential cross sections show similar behaviors: there is a highest platform within a very small scattering angle, beyond which the differential cross sections decrease as the scattering angle increases and lots of oscillating structures appear, where the scattering angle of the first structure decreases as E-P(-1/2) with the increment of the projectile energy E-P; and the structure and amplitude of the differential cross sections are sensitive to the orientation of molecule H-2, which provides a possibility to identify the orientations of molecule H-2 by the vibrational state-selective differential scattering processes.

多电荷态硫离子与氦原子和氢分子碰撞中的多电子转移过程研究

本工作采用反冲离子飞行时间技术和散射离子位置灵敏探测技术，实验研究了Sq+离子与He、H2碰撞中的多电子转移过程和分子离子的碎裂现象。研究了转移电离截面与单电子俘获截面比值和入射离子损失一个电子和两个电子的情况下，靶原子双重电离与单重电离的截面比值随入射离子能量和入射离子电荷态的变化规律，并对不同的碰撞体系的结果进行了比较。研究发现：在本工作研究的入射离子能区，对于HZ分子靶，双电子俘获自电离反应道：S2+H2→S(q-l)+2H++e-。是转移电离过程的主要贡献，而直接转移电离的贡献可以忽略；随着入射离子电荷态的增加，双电子俘获自电离的贡献增加，直接转移电离的贡献逐渐减小，但双电子俘获自电离的贡献的增加比理论预言的要慢。建立了蒙特卡罗程序模拟离子与分子碰撞中产生的具有不同的初始动能的离子碎片的飞行时间谱，深入分析和研究了Sq＋与H2分子碰撞中产生的H2+的解离过程和库仑爆炸过程，以及H＋碎片的能量分布。模拟结果与实验测量到的TOF谱的分析比较说明：在Sq＋与H2分子碰撞实验中，库仑爆炸是产生H+的主要反应道，而氢分子离子H2+发生解离产生H+的反应道相对很弱。

Syntheses and crystal structures of mononuclear rhodium hydrido complexes from the reactions of [Rh(H)(2)(PPh3)(2)(EtOH)(2)]ClO4 with various nitrogen ligands

Reactions of the Rh hydrido complex [Rh(H)(2)(PPh3)(2)(EtOH)(2)]ClO4 (1) With nitrogen ligands such as 2-(4-thiazolyl)benzimidazole (tbz). pyridazine (pdz), imidazole (im) and pyrimidine (pmd) in CH,Cl, afforded Various mononuclear Rh hydrido complexes, [Rh(H)(2)(PPh3)(2)(tbz)]CIO4 (2), [Rh(H)(2)(PPh3)(2)(pdZ)(2)]ClO(4)(.)2CH(2)Cl(2) (3). [Rh(H)Cl(PPh3)(2)(pdz)(2)](ClO4CH2Cl2)-C-. (4). [Rh(H)(2)(PPh3)(2)(im)(2)]ClO(4)(.)2CH(2)Cl(2) (5). [Rh(H)Cl(PPh3)(2)(im)(2)](ClO4CH2Cl2)-C-. (6). [Rh(H)(2)(PPh3)(2)(pmd)(2)](ClO4CH2Cl2)-C-. (7) and the Rh non-hydrido complex [RhCl2(pmd)(4)]ClO4 (8). The Rh complexes 2. 3, 5 and 6 were crystallographically characterized. The formation process was monitored by H-1 NMR and UV-Vis spectra. In all the Rh hydrido complexes, the Rh atom is coordinated by two PPh3. ligands in trans-positions and two nitrogen ligands in the cis-positions. The remaining sites Lire occupied by one or two hydride atoms to form a saturated 18-electron framework in a slightly distorted octahedral geometry. For complex 2 an appreciable inter-molecular pi interaction is observed between planes of tbz and PPh3 ligands, while an intra-molecular hydrogen bonding interaction between C-H and Cl atoms is found in complex 6.