Role of tunneling of hydrogen in photoenolization of a ketone

Photoenolization of a ketone in its lowest triplet state was examined using the AM 1 semiempirical molecular orbital method with complete geometry optimization at the configuration interaction level in the restricted Hartree–Fock frame. The theoretical barrier fits with a polynomial given by Eq. (1) and the probability of tunneling of hydrogen was calculated by the WKB method. The density of states above the zero-point level was estimated by the Whitten–Rabinovitch approximation. Rate constants for the hydrogen and deuterium-abstraction processes via tunneling were then computed at different temperatures. © 1994 John Wiley & Sons, Inc.     

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.     

The palladium-catalyzed cross-coupling reaction of carboxylic anhydrides with arylboronic acids: a DFT study

The mechanism of the cross-coupling of phenylboronic acid with acetic anhydride, a viable model of the widely used Suzuki reaction, has been studied by DFT calculations at the BP86/6-31G level of theory. Two alternative catalytic cycles have been investigated, one starting from a neutral Pd(0)L(2) complex, the other from an anionic "Jutand-type" [Pd(0)L(2)X](-) species. The reaction profiles are in good agreement with the experimental findings, as both pathways require only moderate activation energies. Both pathways are dominated by cis-configured square-planar palladium(II)diphosphine intermediates. Despite careful investigations, we did not find in this model reaction any evidence for five-coordinate palladium(II) intermediates, which are commonly believed to cause the profound effects of counterions in palladium-catalyzed transformations. Instead, our calculations suggest that the higher catalytic activity of anionic complexes, such as [Pd(PMe(3))(2)OAc](-), may arise from their stronger ability to coordinate to carbon electrophiles. The transmetalation sequence is the same for both catalytic cycles, involving the dissociation of one phosphine ligand from the palladium. In the decisive transition state, in which the phenyl group is transferred from boron to palladium, the acetate base is found to be in a bridging coordination between these two atoms.     

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.     

Orientational order in liquid crystals exhibited by some binary mixtures of rod-like and bent-core molecules

We report measurements of the temperature variations of the optical birefringence in the nematic (N) and partial bilayer SmA (SmA_d) phases in 4-n-octyloxy 4^′ -cyanobiphenyl made of rod-like (R) molecules and five mixtures of this compound with 1,3-phenylene bis[4-(3-methylbenzoyloxy)] 4^′ -n- dodecylbiphenyl 4^′ -carboxylate, made of bent-core (BC) molecules. The birefringence decreases with the concentration x of the BC molecules but the macroscopic order parameter initially decreases upto 11mol% of BC molecules and subsequently increases with x . This is attributed to the possible formation of polar clusters of BC molecules. Orientation of BC molecules changes between the N and SmA_d phases and the birefringence data in the two phases imply that the kink angle of the BC molecules is ∼ 90^° rather than ∼ 110^° as obtained from calculations which minimize the energy of the molecule. IR spectroscopic measurements on the mixture with 11mol% of BC molecules have been used to estimate the molecular order parameter S of the R molecules, and to provide additional support for a relatively small kink angle of BC molecules.     

Design of medium energy beam transport line between the RFQ and the Linac in the radioactive ion beam facility at VECC,Kolkata

The design of a medium energy beam transport (MEBT) line comprising of a re-buncher and four quadrupoles, two upstream and the other two downstream of the re-buncher, has been presented. The design was done to ensure almost 100% transport of heavy-ion beams of about 99 keV/u energy from RFQ having a q/A not less than 1/14 through the re-buncher and then through IH Linac of about 0.6 m length in which beam would be accelerated to about 185 keV/u. The re-buncher has been designed to operate at 37.8 MHz, the resonating frequency of both the RFQ and the IH Linac. The entire beam line has been installed and recently O⁵⁺ beam from RFQ has been transported through the re-buncher and subsequently accelerated in the IH Linac successfully.     

Numerical simulation of electromagnetic acoustic transducers using distributed point source method

In spite of many advances in analytical and numerical modeling techniques for solving different engineering problems, an efficient solution technique for wave propagation modeling of an electromagnetic acoustic transducer (EMAT) system is still missing. Distributed point source method (DPSM) is a newly developed semi-analytical technique developed since 2000 by Placko and Kundu (2007) [12] that is very powerful and straightforward for solving various engineering problems, including acoustic and electromagnetic modeling problems. In this study DPSM has been employed to model the Lorentz type EMAT with a meander line and flat spiral type coil. The problem of wave propagation has been solved and eddy currents and Lorentz forces have been calculated. The displacement field has been obtained as well. While modeling the Lorentz force the effect of dynamic magnetic field has been considered that most current analyses ignore. Results from this analysis have been compared with the finite element method (FEM) based predictions. It should be noted that with the current state of knowledge this problem can be solved only by FEM.     

Nature of Nonlocality in Triangle Network based on Elegant Joint Measurement

Defining nonlocality in a no-input closed quantum network scenario is a new area of interest nowadays. Gisin, in [Entropy 21, 325 (2019)], proposed a possible condition for non-tri-locality of the trivial no-input closed network scenario, triangle network, by introducing a new kind of joint measurement bases and a probability bound. In [npj Quantum Information (2020) 6:70] they found a shred of numerical evidence in support of Gisin's probability bound. Now based on that probability bound, it finds the nature of the correlation in a triangle network scenario. This study observes how far the probability lies from that Gisin's bound with every possible combination of entangled and local pure states distributed from three independent quantum sources. Here, it uses the generalized Elegant Joint Measurements bases for each party and find that there is a dependency of non-locality on the entanglement of these joint measurement bases. It also checks the probability bound for the polygon structure.