Accurate time dependent wave packet calculations for the N + OH reaction

We present accurate quantum calculations of state-to-state cross sections for the N + OH → NO + H reaction performed on the ground (3)A' global adiabatic potential energy surface of Guadagnini et al. [J. Chem. Phys. 102, 774 (1995)]. The OH reagent is initially considered in the rovibrational state ν = 0, j = 0 and wave packet calculations have been performed for selected total angular momentum, J = 0, 10, 20, 30, 40,...,120. Converged integral state-to-state cross sections are obtained up to a collision energy of 0.5 eV, considering a maximum number of eight helicity components, Ω = 0,...,7. Reaction probabilities for J = 0 obtained as a function of collision energy, using the wave packet method, are compared with the recently published time-independent quantum mechanical one. Total reaction cross sections, state-specific rate constants, opacity functions, and product state-resolved integral cross-sections have been obtained by means of the wave packet method for several collision energies and compared with recent quasi-classical trajectory results obtained with the same potential energy surface. The rate constant for OH(ν = 0, j = 0) is in good agreement with the previous theoretical values, but in disagreement with the experimental data, except at 300 K.     

Microwave promoted Suzuki reactions between aroyl chlorides and boronic acids catalyzed by heterogeneous and homogeneous phosphine-free palladium catalysts

Suzuki cross-coupling reactions between arylboronic acids and aroyl chlorides with phosphine-free palladium catalysis under microwave irradiation were performed to obtainment of aromatic ketones in good yields within short times. Heterogeneous and homogeneous catalysts were studied as well as their influence in the reaction selectivity relative to homocoupling of the boronic acids.     

Activity of Closed d-Shells in Noble Metal Atoms

The Periodic Table has the column of the noble gas atoms (He, Ne, Ar, Kr, Xe, Rn) as one of its main pillars. Indeed the inert chemical nature of their closed shell structure is so striking that it is sometimes extended to all such structures. Is it true however that any closed shell, say a closed d-subshell will denote a lack of chemical activity? Take the noble metals for instance, so renowned for their catalytic capacity. Platinum has 10 electrons in its valence shell which makes one of its excited states to be a closed 5d¹⁰–6s⁰ state. Surely this state would not be expected to be crucial to the catalytic activity of platinum, or would it? Or take palladium whose ground state is precisely the 4d¹⁰–5s⁰ state, should we expect that an isolated Pd atom at near zero-point temperature would attack a closed-shell hydrogen molecule efficiently? We shall here show that this is precisely the case; the closed-shell excited states of nickel and platinum are indeed crucial, through symmetry avoided crossings, for their reactivity. Other valuable catalysts as ruthenium depend on their excited states with maximal d-shell occupancy for their activity. The most notable confirmation of this new finding; that closed d-shells are vital to the catalytic activity of noble metals however, is the case of palladium whose closed-shell ground state is indeed capable of attacking hydrogen and hydrocarbon molecules even at temperatures well below 10 K as was predicted theoretically and immediately confirmed experimentally.     

Adsorption of carbon monoxide Au/Pd(1 0 0) alloys in ultrahigh vacuum: Identification of adsorption sites

The adsorption of carbon monoxide is studied on Au/Pd(1 0 0) alloys by means of reflection-absorption infrared spectroscopy (RAIRS) and temperature-programmed desorption (TPD). The alloy was formed by adsorbing a four-monolayer thick gold film on a Pd(1 0 0) substrate and by heating to various temperatures to form alloys with a range of palladium coverages. The alloy was characterized using X-ray photoelectron spectroscopy and the composition of the outermost layer measured using low-energy ion scattering spectroscopy. CO adsorbs on palladium bridge sites only for palladium coverages greater than 0.5 monolayers (ML) suggesting that next-nearest neighbor sites are preferentially populated by palladium atoms. CO adsorbs on atop palladium sites and desorbs at ∼350 K corresponding to a desorption activation energy of ∼117 kJ/mol. However, at lower palladium coverages, these sites are not occupied and CO desorption states are detected 170 and 112 K corresponding to desorption activation energies of ∼53 kJ/mol and ∼35 kJ/mol, respectively, for these states. It is suggested that these states are due to a restructuring of the surface to form low-coordination gold sites that obscure the atop palladium site.     

Dilatometric model for determining the formation of austenite during continuous heating in medium carbon steel

Journal of Thermal Analysis and Calorimetry - A model was developed to predict the formation of austenite and dilatometric behavior during continuous heating in AISI 1045 steel, which has an...     

Free Subordination and Belinschi–Nica Semigroup

We realize the Belinschi–Nica semigroup of homomorphisms as a free multiplicative subordination. This realization allows to define more general semigroups of homomorphisms with respect to free multiplicative convolution. For these semigroups we show that a differential equation holds, generalizing the complex Burgers equation. We give examples of free multiplicative subordination and find a relation to the Markov–Krein transform, Boolean stable laws and monotone stable laws. A similar idea works for additive subordination, and in particular we study the free additive subordination associated to the Cauchy distribution and show that it is a homomorphism with respect to monotone, Boolean and free additive convolutions.     

Microwave‐assisted synthesis of 2‐(2‐pyridyl)azoles. Study of their corrosion inhibiting properties

An efficient and fast procedure for the synthesis of 2‐(2‐pyridyl)azoles is described using ionic liquids as catalysts under microwave irradiation. The X‐ray crystallographic analyses for three of the four synthesized compounds are presented. Potentiodynamic polarization studies were carried out to analyze the electrochemical behavior of the compounds in corrosive acidic media. Of the four derivatives, one compound was detected to be an effective corrosion inhibitor prototype for oil refinery environments.     

Calculating the surface tension between a flat solid and a liquid: a theoretical and computer simulation study of three topologically different methods

We discuss three topologically different methods for calculating the surface tension between a flat solid and a liquid from theoretical and computer simulation viewpoints. The first method, commonly used in experiments, measures the contact angle at which a static droplet of liquid rests on a solid surface. We present a new analysis algorithm for this method and explore the effects of line tension on the contact angle. The second method, commonly used computer simulations, uses the pressure tensor through the virial in a system where a thick, infinitely extended slab of liquid rests on a solid surface. The third method, which is original to this paper and is closest to the thermodynamic definition of surface tension, applies to a spherical solid in contact with liquid in which the flat solid is recovered by extrapolating the sphere radius to infinity. We find that the second and third methods agree with each other, while the first method systematically underestimates surface tension values.