Effect of water and air-water interface on the structural modification of Ni-arachidate Langmuir-Blodgett films

Nickel arachidate (NiA) Langmuir-Blodgett (LB) films have been deposited on hydrophilic Si(0 0 1) substrates by three (up-down-up) and five (up-down-up-down-up) strokes. During deposition, substrates were kept inside the water subphase for different times after each down stroke. Structural information of all the LB films have been obtained from X-ray reflectivity (XRR) studies. One and two symmetric monolayer (SML) was deposited on top of the asymmetric monolayer (AML) in three and five stokes respectively. All the preformed LB films were then used to go through the air-water interface with the same speed that was used at the time of film deposition. Structural information obtained from the XRR studies show that mainly the top layer density decreases after passing through the air-water interface but the layered structure remains the same. Information obtained from both the XRR and atomic force microscopy (AFM) studies suggest that molecules peeled from the top SML layer do not reincorporate with the LB film through tail-tail hydrophobic interaction. Our study shows that NiA LB film has better stability compared with cadmium arachidate LB film inside the water subphase without forming any out-of-plane molecular reorganization.     

Redox-rich spin-spin-coupled semiquinoneruthenium dimers with intense near-IR absorption

Using the [RuCl(μ-tppz)ClRu](2+) [tppz = 2,3,5,6-tetrakis(2-pyridyl)pyrazine] platform for bridging two o-quinone/catecholate two-step redox systems (unsubstituted, Q(n), or 3,5- di-tert-butyl-substituted, DTBQ(n)), we have obtained the stable complexes [(Q(?-))Ru(II)Cl(μ-tppz)ClRu(II)(Q(?-))] (1) and the structurally characterized [(DTBQ(?-))Ru(II)Cl(μ-tppz)ClRu(II)(DTBQ(?-))] (2). The compounds exhibit mostly quinone-ligand-based redox activity within a narrow potential range, high-intensity near-IR absorptions (λ(max) ≈ 920 nm; ε > 50,000 M(-1) cm(-1)), and variable intra- and intermolecular spin-spin interactions. Density functional theory calculations, electron paramagnetic resonance (EPR), and spectroelectrochemical results (UV-vis-near-IR region) for three one-electron-reduction and two one-electron-oxidation processes were used to probe the electronic structures of the systems in the various accessible valence states. EPR spectroscopy of the singly charged doublet species showed semiquinone-type response for 1(+), 2(+), and 2(-), while 1 exhibits more metal based spin, a consequence of the easier reduction of Q as compared to DTBQ. Comparison with the analogous redox series involving a more basic N-phenyliminoquinone ligand reveals significant differences related to the shifted redox potentials, different space requirements, and different interactions between the metals and the quinone-type ligands. As a result, the tppz bridge is reduced here only after full reduction of the terminal quinone ligands to their catecholate states.     

Magnetic exchange interactions and magneto-structural correlations in heterobridged μ-phenoxo-μ(1,1)-azide dinickel(II) compounds: a combined experimental and theoretical exploration

This investigation presents the syntheses, crystal structures, magnetic properties, and density functional theoretical modeling of magnetic behavior of two heterobridged μ-phenoxo-μ(1,1)-azido dinickel(II) compounds [Ni(II)(2)(L(1))(2)(μ(1,1)-N(3))(N(3))(H(2)O)]·CH(3)CH(2)OH (1) and [Ni(II)(2)(L(2))(2)(μ(1,1)-N(3))(CH(3)CN)(H(2)O)](ClO(4))·H(2)O·CH(3)CN (2), where HL(1) and HL(2) are the [1+1] condensation products of 3-methoxysalicylaldehyde and 1-(2-aminoethyl)-piperidine (for HL(1))/4-(2-aminoethyl)-morpholine (for HL(2)), along with density functional theoretical magneto-structural correlations of μ-phenoxo-μ(1,1)-azido dinickel(II) systems. Compounds 1 and 2 crystallize in orthorhombic (space group Pbca) and monoclinic (space group P2(1)/c) systems, respectively. The coordination environments of both metal centers are distorted octahedral. The variable-temperature (2-300 K) magnetic susceptibilities at 0.7 T of both compounds have been measured. The interaction between the metal centers is moderately ferromagnetic; J = 16.6 cm(-1), g = 2.2, and D = -7.3 cm(-1) for 1 and J = 16.92 cm(-1), g = 2.2, and D(Ni1) = D(Ni2) = -6.41 cm(-1) for 2. Broken symmetry density functional calculations of exchange interaction have been performed on complexes 1 and 2 and provide a good numerical estimate of J values (15.8 cm(-1) for 1 and 15.35 cm(-1) for 2) compared to experiments. The role of Ni-N bond length asymmetry on the magnetic coupling has been noted by comparing the structures and J values of complexes 1 and 2 together with previously published dimers 3 (Eur. J. Inorg. Chem. 2009, 4982), 4 (Inorg. Chem. 2004, 43, 2427), and 5 (Dalton Trans. 2008, 6539). Our extensive DFT calculations reveal an important clue to the mechanism of coupling where the orientation of the magnetic orbitals seems to differ with asymmetry in the Ni-N bond lengths. This difference in orientation leads to a large change in the overlap integral between the magnetic orbitals and thus the magnetic coupling. DFT calculations have also been extended to develop several magneto-structural correlations in this type of complexes and the correlation aim to focus on the asymmetry of the Ni-N bond lengths reveal that the asymmetry plays a proactive role in governing the magnitude of the coupling. From a completely symmetric Ni-N bond length, two behaviors have been noted: with a decrease in bond length there is an increase in the ferromagnetic coupling, while an increase in the bond lengths leads to a decrease in ferromagnetic interaction. The later correlation is supported by experiments. The magnetic properties of 1, 2, and three previously reported related compounds have been discussed in light of the structural parameters and also in light of the theoretical correlations determined here.     

Baryogenesis at the electroweak scale

The generation of the baryon asymmetry of the universe is considered in the standard model of the electroweak theory with simple extensions of the Higgs sector. The propagation of quarks of masses up to about 5 GeV are considered, taking into account their markedly different dispersion relations due to propagation through the hot electroweak plasma. It is shown that the contribution of the b quark to the baryon asymmetry can be comparable to that for the t quark considered earlier.     

Two-potential formula continued off-the-energy-shell

We derive an off-energy-shell generalization of the two-potential formula by using a coordinate-space approach and apply the formalism to construct algorithms for studying spatial behaviour of the fully off-shellT matrix. We also suggest some future applications of the proposed theory.     

A theoretical analysis of acoustic microscopy with converging acoustic beams

A theoretical analysis is carried out to synthesize acoustic material signatures (AMS) of solid plates immersed in water. The distinctive feature of this analysis is that it avoids three major simplifying assumptions of the presently available techniques, which are, paraxial approximation, assumption of perfect reflection and Gaussian summation of the incident field. Presently available techniques can avoid some but not all of these simplifying assumptions for computing the AMS. In this paper the analysis is carried out for lowfrequency acoustic waves generated by a cylindrical transducer without a lens rod. Reasons for these changes in the conventional acoustic microscope geometry is given. The AMS is synthesized for an aluminium plate in presence as well as in absence of water on its one side. As expected a significant difference is observed between the signatures generated under these two situations.     

A factorization theorem for a certain class of graphs

In this note we give a necessary and sufficient condition for factorization of graphs satisfying the “odd cycle property”. We show that a graph G with the odd cycle property contains a [k_i] factor if and only if the sequence [H]+[k_i] is graphical for all subgraphs H of the complement of G.A similar theorem is shown to be true for all digraphs.     

Bounds on the number of disjoint spanning trees

It is shown that an n-edge connected graph has at least ?$\text{(n ? 1)}\text{2}$? pairwise edge-disjoint spanning trees. This bound is best possible in general. A maximal planar graph with four or more vertices contains two edge-disjoint spanning trees. For a maximal toroidal graph, this number is three.     

Detection of kissing bonds by Lamb waves

Closed cracks under compressive normal stresses are difficult to detect by the conventional ultrasonic techniques. When the crack surfaces stay in very close contact with each other then the bond between the two surfaces of the crack is called a ‘kissing bond’. This is a very dangerous bond. Catastrophic failures can result if the system is subjected to crack opening normal stresses or shear stresses. When the crack surfaces are smooth then kissing bonds cannot transmit shear stress very well but can carry compressive normal stress, these bonds are called ‘slip bonds’. Conventional P-wave scans (C-scan or A-scan) are based on the assumptions that P-waves are reflected by the defective interface. However, an interface subjected to a large compressive stress cannot reflect P-waves effectively, hence these bonds remain invisible to the conventional P-wave based C-scan or A-scan techniques. In this paper it is shown that the kissing bonds can be effectively detected by some leaky Lamb mode. Theoretical and experimental results are presented to show that using the Lamb waves is an effective way of detecting kissing bonds.