Site symmetry dependence of repulsive interactions between chemisorbed oxygen atoms on Pt{100}-(1x1)

Ab initio total energy calculations using density functional theory with the generalized gradient approximation have been performed for the chemisorption of oxygen atoms on a Pt{100}-(1 x 1) slab. Binding energies for the adsorption of oxygen on different high-symmetry sites are presented. The bridge site is the most stable at a coverage of 0.5 ML, followed by the fourfold hollow site. The atop site is the least stable. This finding is rationalized by analyzing the ''local structures'' formed upon oxygen chemisorption. The binding energies and heats of adsorption at different oxygen coverages show that pairwise repulsive interactions are considerably stronger between oxygen atoms occupying fourfold sites than those occupying bridge sites. Analysis of the partial charge densities associated with Bloch states demonstrates that the O-Pt bond is considerably more localized at the bridge site. These effects cause a sharp drop in the heats of adsorption for oxygen on hollow sites when the coverage is increased from 0.25 to 0.5 ML. Mixing between oxygen p orbitals and Pt d orbitals can be observed over the whole metal d-band energy range.

BUCKLED LAYER STRUCTURE FOR ATOMIC ADSORPTION ON W(100) - THE (ROOT-2X-ROOT-2)R45-DEGREES NITROGEN STRUCTURE FROM ATLEED

Adsorption of 0.5 monolayer of N adatoms on W{100} results in a sharp (root 2 X root 2)R45 degrees LEED pattern. The only previous quantitative LEED study of this system gave a simple overlayer model with a Pendry R-factor of 0.55. An exhaustive search has been made of possible structures, including a novel vacancy reconstruction, displacive reconstructions and underlayer adsorption. From this work a new overlayer structure is derived with an R(p) value of 0.22, displaying a considerable buckling of 0.27 +/- 0.05 Angstrom within the second W layer and consequently involving large changes in the interlayer spacings of the surface. The N adatom is pseudo-five-fold coordinated to the W surface, bonding to a second-layer W atom with a nearest-neighbour bond length of 2.13 Angstrom and with the four next-nearest-neighbour W atoms in the surface plane at 2.27 Angstrom. The structure does not resolve the work function anomaly observed on this surface.

HOLOGRAPHIC IMAGES OF IODINE ATOMS ON A SILVER SURFACE FROM ELECTRON-EMISSION PATTERNS

BARTON 1 has suggested that photoelectron interference patterns may be used directly as holograms to obtain atomic-resolution images of surface structures. Bulk structures have been obtained previously by this means from experimental patterns of high-energy Kikuchi(quasi-elastically scattered) and Auger electrons 2,3. Here we test the feasibility of this technique for determination of surface structures using Auger intensity patterns obtained 4,5 from iodine chemisorbed on a pseudomorphic silver monolayer on Pt{111}. By direct numerical holographic inversion, we obtain three-dimensional images which show that iodine adatoms are located in hollows of 3-fold symmetry on the surface. The images yield the site symmetry with good atomic resolution in the surface plane, but suffer from poor resolution along the Ag-I axis. We anticipate that data with better angular resolution obtained at low temperatures would improve the spatial resolution of such images.

THE SURFACE-STRUCTURE OF A C(2 X-2) POTASSIUM OVERLAYER ON CO(1010)

The surface structure of the clean Co{1010BAR} surface and a c(2 x 2) potassium overlayer have been determined by quantitative low energy electron diffraction. The Co{1010BAR} sample has been shown to be laterally unreconstructed with the surface being uniquely terminated by an outermost closely packed double layer (dz12 = 0.68 angstrom). A damped oscillatory relaxation of the outermost three atomic layers occurs, with relaxations DELTA-dz12 = -6.5 +/- 2% and DELTA-dz23 = +1.0 +/- 2%.

The c(2 x 2) overlayer formed at a coverage of 0.5 ML was subjected to a full I-V analysis. A range of adsorption sites were tested including fourfold hollow, on-top, and both long and short bridge sites in combination with both "long" and "short" cobalt interlayer terminations. A clear preference was found for adsorption in the maximal coordination fourfold hollow site. No switching of surface termination occurs. The potassium adatoms reside in the [1210BAR] surface channels directly above second layer cobalt atoms with a potassium to outermost cobalt interlayer separation of 2.44 +/- 0.05 angstrom. Potassium-cobalt bond lengths of 3.40 +/- 0.05 and 3.12 +/- 0.05 angstrom between the four (one) outermost (second) layer nearest-neighbour substrate atoms suggests a potassium effective radius of 1.87 +/- 0.05 angstrom, somewhat smaller than the Pauling covalent radius and considerably larger than the ionic radius (1.38 angstrom). The alkali-surface bonding is thus predominantly "covalent"/"metallic".

Homo-and heteropolymetallic 3-(2-pyridyl)pyrazolate manganese and rhenium complexes

fac-[MBr(CO)(3)(pypzH)] (M = Mn, Re; pypzH = (3-(2-pyridyl) pyrazole) complexes are prepared from fac[ MBr(CO)(3)(NCMe)(2)] and pypzH. The result of their deprotonation depends on the metallic substrate: the rhenium complex affords cleanly the bimetallic compound [fac-{Re(CO)(3)(mu(2)-pypz)}] 2 (mu(2)-pypz = mu(2)-3-(2pyridyl-. 1N) pyrazolate-2. 1N), which was crystallographically characterized, whereas a similar manganese complex was not detected. When two equivalents of pyridylpyrazolate are used, polymetallic species [fac-M(CO) 3(mu(2)-pypz)(mu(3)-pypz) M'] (mu(3)-pypz = mu(3)-3-(2-pyridyl-kappa N-1) pyrazolate-1 kappa 2N, N: 2. 1N:; M = Mn, M' = Li, Na, K; M = Re, M' = Na) are obtained. The crystal structures of the manganese carbonylate complexes were determined. The lithium complex is a monomer containing one manganese and one lithium atom, whereas the sodium and potassium complexes are dimers and reveal an unprecedented coordination mode for the bridging 3-(2-pyridyl) pyrazolate ligand, where the nitrogen of the pyridyl fragment and the nitrogen-1 of pyrazolate are chelated to manganese atoms, and each nitrogen-2 of pyrazolate is coordinated to two alkaline atoms. The polymetallic carbonylate complexes are unstable in solution and evolve spontaneously to [fac-{Re(CO) 3(mu(2)-pypz)}](2) or to the trimetallic paramagnetic species [MnII(mu(2)-pypz) 2{fac-{MnI(CO) 3(mu(2)-pypz)}(2)}]. The related complex cis-[MnCl2(pypzH)(2)] was also synthesized and structurally characterized. The electrochemical behavior of the new homo-and heteropolymetallic 3-(2-pyridyl) pyrazolate complexes has been studied and details of their redox properties are reported.

Bits, Atoms, and Information Sharing: new opportunities for participation

The particular characteristics and affordances of technologies play a significant role in human experience by defining the realm of possibilities available to individuals and societies. Some technological configurations, such as the Internet, facilitate peer-to-peer communication and participatory behaviors. Others, like television broadcasting, tend to encourage centralization of creative processes and unidirectional communication. In other instances still, the affordances of technologies can be further constrained by social practices. That is the case, for example, of radio which, although technically allowing peer-to-peer communication, has effectively been converted into a broadcast medium through the legislation of the airwaves. How technologies acquire particular properties, meanings and uses, and who is involved in those decisions are the broader questions explored here. Although a long line of thought maintains that technologies evolve according to the logic of scientific rationality, recent studies demonstrated that technologies are, in fact, primarily shaped by social forces in specific historical contexts. In this view, adopted here, there is no one best way to design a technological artifact or system; the selection between alternative designs—which determine the affordances of each technology—is made by social actors according to their particular values, assumptions and goals. Thus, the arrangement of technical elements in any technological artifact is configured to conform to the views and interests of those involved in its development. Understanding how technologies assume particular shapes, who is involved in these decisions and how, in turn, they propitiate particular behaviors and modes of organization but not others, requires understanding the contexts in which they are developed. It is argued here that, throughout the last century, two distinct approaches to the development and dissemination of technologies have coexisted. In each of these models, based on fundamentally different ethoi, technologies are developed through different processes and by different participants—and therefore tend to assume different shapes and offer different possibilities. In the first of these approaches, the dominant model in Western societies, technologies are typically developed by firms, manufactured in large factories, and subsequently disseminated to the rest of the population for consumption. In this centralized model, the role of users is limited to selecting from the alternatives presented by professional producers. Thus, according to this approach, the technologies that are now so deeply woven into human experience, are primarily shaped by a relatively small number of producers. In recent years, however, a group of three interconnected interest groups—the makers, hackerspaces, and open source hardware communities—have increasingly challenged this dominant model by enacting an alternative approach in which technologies are both individually transformed and collectively shaped. Through a in-depth analysis of these phenomena, their practices and ethos, it is argued here that the distributed approach practiced by these communities offers a practical path towards a democratization of the technosphere by: 1) demystifying technologies, 2) providing the public with the tools and knowledge necessary to understand and shape technologies, and 3) encouraging citizen participation in the development of technologies.

Quantum Monte Carlo study of electrostatic polarizabilities of H and He atoms /

The infinitesimal differential quantum Monte Carlo (QMC) technique is used to estimate electrostatic polarizabilities of the H and He atoms up to the sixth order in the electric field perturbation. All 542 different QMC estimators of the nonzero atomic polarizabilities are derived and used in order to decrease the statistical error and to obtain the maximum efficiency of the simulations. We are confident that the estimates are "exact" (free of systematic error): the two atoms are nodeless systems, hence no fixed-node error is introduced. Furthermore, we develope and use techniques which eliminate systematic error inherent when extrapolating our results to zero time-step and large stack-size. The QMC results are consistent with published accurate values obtained using perturbation methods. The precision is found to be related to the number of perturbations, varying from 2 to 4 significant digits.

Asymmetric hydrogenation of alkenes with cationic iridium(I) complexes of 2-phosphino-1-aminoferrocene ligands

Iridium complexes with bidentate P,N ligands represent a class of catalysts that significantly expand the application range of asymmetric hydrogenation. New substrate classes, for which there have previously been no suitable catalysts, can now be efficiently hydrogenated in high conversion and enantioselectivity. These substrates are often of synthetic importance, thus iridium catalysis represents a significant advance in the field of asymmetric catalysis. Planar chiral ferrocenyl aminophosphine ligands in which both heteroatoms were directly bound to the cyclopentadienyl ring were prepared by BF3-activated lithiationsubstitution in the presence of a chiral diamine in 49-59% yield and 75-85% enantiomeric excess. Some of these ligands were recrystallized to enantiomeric purity via ammonium fluoroborate salt formation of the phosphine sulfide. A crystal structure of one of these compounds was obtained and features an intramolecular hydrogen bond between the nitrogen, hydrogen, and sulfur atoms. Neutralization, followed by desulfurization, provided the free ligands in enantiomeric purity. Iridium complexes with these ligands were formed via reaction with [Ir(COD)Clh followed by anion exchange with NaBArF. These complexes were successfully applied in homogeneous hydrogenation of several prochiral substrates, providing products in up to 92% enantiomeric excess. Variation of the dimethyl amino group to a pyrrolidine group had a negative effect on the selectivity of hydrogenation. Variation of the substituents on phosphorus to bulkier ortho-tolyl groups had a positive effect, while variation to the more electron rich dicyclohexyl phosphine had a negative effect on selectivity.

Synthesis and Characterisation of New Transition Metal Complexes of Schiff Bases Derived from 3-hydroxyquinoxaline-2- carboxaldehyde and Application of Some ofthese Complexes as Hydrogenation and Oxidation Catalysts

The thesis deals with studies on the synthesis, characterisation and catalytic applications of some new transition metal complexes of the Schiff bases derived from 3-hydroxyquinoxaline 2-carboxaldehyde.. Schiff bases which are considered as ‘privileged ligands’ have the ability to stabilize different metals in different oxidation states and thus regulate the performance of metals in a large variety of catalytic transformations. The catalytic activity of the Schiff base complexes is highly dependant on the environment about the metal center and their conformational flexibility. Therefore it is to be expected that the introduction of bulky substituents near the coordination sites might lead to low symmetry complexes with enhanced catalytic properties. With this view new transition metal complexes of Schiff bases derived from 3-hydroxyquinoxaline-2-carboxaldehyde have been synthesised. These Schiff bases have more basic donor nitrogen atoms and the presence of the quinoxaline ring may be presumed to build a favourable topography and electronic environment in the immediate coordination sphere of the metal. The aldehyde was condensed with amines 1,8-diaminonaphthalene, 2,3-diaminomaleonitrile, 1,2-diaminocyclohexane, 2-aminophenol and 4-aminoantipyrine to give the respective Schiff bases. The oxovanadium(IV), copper(II) and ruthenium(II)complexes of these Schiff bases were synthesised and characterised. All the oxovanadium(IV) complexes have binuclear structure with a square pyramidal geometry. Ruthenium and copper form mononuclear complexes with the Schiff base derived from 4- aminoantipyrine while binuclear square planar complexes are formed with the other Schiff bases. The catalytic activity of the copper complexes was evaluated in the hydroxylation of phenol with hydrogen peroxide as oxidant. Catechol and hydroquinone are the major products. Catalytic properties of the oxovanadium(IV) complexes were evaluated in the oxidation of cyclohexene with hydrogen peroxide as the oxidant. Here allylic oxidation products rather than epoxides are formed as the major products. The ruthenium(II) complexes are found to be effective catalysts for the hydrogenation of benzene and toluene. The kinetics of hydrogenation was studied and a suitable mechanism has been proposed.

Copper(II) complexes of N(4)-substituted thiosemicarbazones derived from pyridine-2-carbaldehyde: Crystal structure of a binuclear complex

Ten copper(II) complexes {[CuL1Cl] (1), [CuL1NO3]2 (2), [CuL1N3]2 · 2/3H2O (3), [CuL1]2(ClO4)2 · 2H2O (4), [CuL2Cl]2 (5), [CuL2N3] (6), [Cu(HL2)SO4]2 · 4H2O (7), [Cu(HL2)2] (ClO4)2 · 1/2EtOH (8), [CuL3Cl]2 (9), [CuL3NCS] · 1/2H2O (10)} of three NNS donor thiosemicarbazone ligands {pyridine-2-carbaldehyde-N(4)-p-methoxyphenyl thiosemicarbazone [HL1], pyridine-2-carbaldehyde-N(4)-2-phenethyl thiosemicarbazone [HL2] and pyridine-2-carbaldehyde N(4)-(methyl), N(4)-(phenyl) thiosemicarbazone [HL3]} were synthesized and physico-chemically characterized. The crystal structure of compound 9 has been determined by X-ray diffraction studies and is found that the dimer consists of two square pyramidal Cu(II) centers linked by two chlorine atoms.

Structural and spectral studies of novel Co(III) complexes of N(4)-substituted thiosemicarbazones derived from pyridine-2-carbaldehyde

Seven bis(ligand) Co(III) complexes {[CoL21] NO3 · H2 O (1), [CoL21] Cl · 2 H2 O (2),[CoL21] ClO4 (3), [CoL22] NO3 (4), [CoL22] Cl · 2 H2 O (5), [CoL23] Br · 2 H2 O (6), [CoL23] ClO4 · H2 O (7)} of three thiosemicarbazone ligands {pyridine-2-carbaldehyde-N(4)-p-methoxyphenyl thiosemicarbazone [HL1], pyridine-2-carbaldehyde-N(4)-2-phenylethyl thiosemicarbazone [HL2] and pyridine-2-carbaldehyde-N(4)-(methyl),N(4)-(phenyl) thiosemicarbazone [HL3]} were synthesized and physico-chemically characterized. All complexes are assigned octahedral geometries on the basis of spectral studies. The ligands deprotonate and coordinate by means of pyridine nitrogen, azomethine nitrogen, and thiolate sulfur atoms. The single crystal X-ray structures of HL3 and two nitrate compounds are discussed. The structural studies corroborate the spectral characterization.

Copper(II) complexes derived from di-2-pyridyl ketone-N4-phenyl-3-semicarbazone: Synthesis and spectral studies

Five copper(II) complexes [CuLCl]2·CuCl2·4H2O (1), [CuLOAc] (2), [CuLNO3]2 (3), [CuLN3] (4) and [CuLNCS]·3/2H2O (5) of di-2-pyridyl ketone-N4-phenyl-3-semicarbazone (HL) were synthesized and characterized by elemental analyses and electronic, infrared and EPR spectral techniques. In all these complexes the semicarbazone undergoes deprotonation and coordinates through enolate oxygen, azomethine and pyridyl nitrogen atoms. All the complexes are EPR active due to the presence of an unpaired electron. EPR spectra of all the complexes in DMF at 77K suggest axial symmetry and the presence of half field signals for the complexes 1 and 3 indicates dimeric structures

(E)-2-(4-Benzyloxy-2-hydroxybenzylidene)- N-phenylhydrazinecarbothioamide

The title compound, C21H19N3O2S, exists in the thione form. The configuration about the C N bond is E. The hydrazinecarbothioamide unit adopts an almost planar arrangement, with maximum deviations of 0.016 (3) and 0.016 (2) A ° for the two thiourea N atoms. An intramolecular O—H N hydrogen bond occurs. Weak intermolecular N— H S, C—H O and C—H interactions are observed in the crystal structure

Studies on the interaction of two level atoms with quantized electromagnetic field

The present study described about the interaction of a two level atom and squeezed field with time varying frequency. By applying a sinusoidal variation in the frequency of the field, the randomness in population inversion is reduced and the collapses and periodic revivals are regained. Quantum optics is an emerging field in physics which mainly deals with the interaction of atoms with quantised electromagnetic fields. Jaynes-Cummings Model (JCM) is a key model among them, which describes the interaction between a two level atom and a single mode radiation field. Here the study begins with a brief history of light, atom and their interactions. Also discussed the interaction between atoms and electromagnetic fields. The study suggest a method to manipulate the population inversion due to interaction and control the randomness in it, by applying a time dependence on the frequency of the interacting squeezed field.The change in behaviour of the population inversion due to the presence of a phase factor in the applied frequency variation is explained here.This study also describes the interaction between two level atom and electromagnetic field in nonlinear Kerr medium. It deals with atomic and field state evolution in a coupled cavity system. Our results suggest a new method to control and manipulate the population of states in two level atom radiation interaction,which is very essential for quantum information processing.We have also studied the variation of atomic population inversion with time, when a two level atom interacts with light field, where the light field has a sinusoidal frequency variation with a constant phase. In both coherent field and squeezed field cases, the population inversion variation is completely different from the phase zero frequency modulation case. It is observed that in the presence of a non zero phase φ, the population inversion oscillates sinusoidally.Also the collapses and revivals gradually disappears when φ increases from 0 to π/2. When φ = π/2 the evolution of population inversion is identical to the case when a two level atom interacts with a Fock state. Thus, by applying a phase shifted frequency modulation one can induce sinusoidal oscillations of atomic inversion in linear medium, those normally observed in Kerr medium. We noticed that the entanglement between the atom and field can be controlled by varying the period of the field frequency fluctuations. The system has been solved numerically and the behaviour of it for different initial conditions and different susceptibility values are analysed. It is observed that, for weak cavity coupling the effect of susceptibility is minimal. In cases of strong cavity coupling, susceptibility factor modifies the nature in which the probability oscillates with time. Effect of susceptibility on probability of states is closely related to the initial state of the system.