Simulation of thermally-induced processes of diffusion and phase formation in layered metal-metalloid systems

A physical model of thermally induced processes of diffusion and phase formation in layered metal-metalloid systems is offered. The software for the model is created, which allows one to quantitatively describe the kinetics of these processes under arbitrary modes of annealing. The results of theoretical computations are compared with the data of experimental studies of a ⁵⁷Fe:O⁺ layered implantation system using the methods of M?ssbauer spectroscopy. The agreement between the numerical and experimental results indicates that the nature of phase transformations in the investigated system is determined by a change in the local concentration of the metalloid during its interstitial diffusion and corresponds to peculiarities of the phase equilibrium diagram of the Fe-O binary system.     

On the long‐range relativistic effects in the 15N NMR chemical shifts of halogenated azines

Long‐range β‐ and γ‐relativistic effects of halogens in ¹⁵N NMR chemical shifts of 20 halogenated azines (pyridines, pyrimidines, pyrazines, and 1,3,5‐triazines) are shown to be unessential for fluoro‐, chloro‐, and bromo‐derivatives (1–2 ppm in average). However, for iodocontaining compounds, β‐ and γ‐relativistic effects are important contributors to the accuracy of the ¹⁵N calculation. Taking into account long‐range relativistic effects slightly improves the agreement of calculation with experiment. Thus, mean average errors (MAE) of ¹⁵N NMR chemical shifts of the title compounds calculated at the non‐relativistic and full 4‐component relativistic levels in gas phase are accordingly 7.8 and 5.5 ppm for the range of about 150 ppm. Taking into account solvent effects within the polarizable continuum model scheme marginally improves agreement of computational results with experiment decreasing MAEs from 7.8 to 7.4 ppm and from 5.5 to 5.3 ppm at the non‐relativistic and relativistic levels, respectively. The best result (MAE: 5.3 ppm) is achieved at the 4‐component relativistic level using Keal and Tozer's KT3 functional used in combination with Dyall's relativistic basis set dyall.av3z with taking into account solvent effects within the polarizable continuum solvation model. The long‐range relativistic effects play a major role (of up to dozen of parts per million) in ¹⁵N NMR chemical shifts of halogenated nitrogen‐containing heterocycles, which is especially crucial for iodine derivatives. This effect should apparently be taken into account for practical purposes.     

Full four‐component relativistic calculations of the one‐bond 77Se–13C spin‐spin coupling constants in the series of selenium heterocycles and their parent open‐chain selenides

Four‐component relativistic calculations of ⁷⁷Se–¹³C spin–spin coupling constants have been performed in the series of selenium heterocycles and their parent open‐chain selenides. It has been found that relativistic effects play an essential role in the selenium–carbon coupling mechanism and could result in a contribution of as much as 15–25% of the total values of the one‐bond selenium–carbon spin‐spin coupling constants. In the overall contribution of the relativistic effects to the total values of ¹J(Se,C), the scalar relativistic corrections (negative in sign) by far dominate over the spin‐orbit ones (positive in sign), the latter being of less than 5%, as compared to the former (ca 20%). A combination of nonrelativistic second‐order polarization propagator approach (CC2) with the four‐component relativistic density functional theory scheme is recommended as a versatile tool for the calculation of ¹J(Se,C). Solvent effects in the values of ¹J(Se,C) calculated within the polarizable continuum model for the solvents with different dielectric constants (ε 2.2–78.4) are next to negligible decreasing negative ¹J(Se,C) in absolute value by only about 1 Hz. The use of the locally dense basis set approach applied herewith for the calculation of ⁷⁷Se–¹³C spin‐spin coupling constants is fully justified resulting in a dramatic decrease in computational cost with only 0.1–0.2‐Hz loss of accuracy. Copyright © 2014 John Wiley & Sons, Ltd.     

Geometries and NMR properties of cisplatin and transplatin revisited at the four-component relativistic level

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Modification of Phenol- and Carbamide-Formaldehyde Resins by Cellulose By-products

To improve their properties, phenol- and carbamide-formaldehyde adhesives were modified by cellulose by-products. It has been shown that the introduction of pectol into phenol-formaldehyde resin of SFZh-3013 grade and products of sulfite-cellulose production into adhesive compositions based on carbamide-formaldehyde resins increases the plywood gluing strength and curing rate.     

Mode manipulation in system of coupled microcavities with whispering gallery modes

In recent years the studies of electromagnetic modes in solid spherical microcavities have been of great interest both for their potential applications and fundamental optical properties. A system of coherently coupled microcavities may be called a “photonic molecule” and can be employed in the tight-binding device in order to manipulate photons in micrometer length scale. In this work we demonstrate the possibility of mode manipulation in systems of symmetric photonic molecules formed by placing several high-Q micro-spheres in contact. We observe photonic nanojets that reflect the symmetry of the photonic molecule, with 3 jets located at 120 degrees with respect to each other for the triangular photonic molecule. A benzene molecule-like structure consisting of a 7-microspheres cyclic photonic molecule shows a field emission pattern similar to the spatial distribution of the orbitals of the benzene molecule. We also present some results showing the coexistence of whispering gallery modes and photonic nanojets in the same structure.     

Quantum-chemical calculations of NMR chemical shifts of organic molecules: XIV. Solvation effects in calculations of chemical shifts in 13C NMR spectra of chlorine-containing compounds

Analysis of precision factors in calculations of ¹³C NMR chemical shifts in the series of saturated and unsaturated organochlorine compounds was performed in the framework of the method of electron density functional theory GIAO-DFT-KT3/pcS-2 in the gas phase and with accounting for solvent effect by the polarized continuum model IEF-PCM. The accounting for solvation effects in calculations of ¹³C NMR chemical shifts within the framework of the IEF-PCM model is not fundamental for organochlorine compounds, yet it considerably improves the precision of calculations up to 2.5 ppm.     

The Influence of Inorganic and Organic Components of Biofilms with Microscopic Fungi on the Phase Composition and Morphology of Crystallizing Calcium Oxalates

Crystallography Reports - The influence of organic and inorganic components of biofilms with microscopic fungi on the phase composition and morphology of precipitating calcium oxalates has been...     

Density functional and spectroscopic studies of nitrogen inversion in substituted dizocilpines

While developing a synthesis towards tagged dizocilpine (MK‐801) analogues, we observed highly restricted inversion of a nitrogen centre in a number hydroxylamines obtained as key intermediates. These compounds are shown to possess some of the structural elements which are expected to significantly hinder the nitrogen inversion, potentially leading to hydroxylamines with a chiral nitrogen centre. Free energy barriers (ΔG^≠) of the nitrogen inversion were estimated to be ca. 22 kcal mol^?1 at temperatures near 420 K using variable temperature NMR measurements in DMSO‐d₆. Further density functional studies of a number model systems were undertaken in order to better rationalize the measured inversion barriers and follow the role of various structural factors in raising the barrier height of the nitrogen inversion process. Copyright © 2008 John Wiley & Sons, Ltd.     

Reduction of amorphous Fe(III)-hydroxide by binary microbial culture, a Mössbauer study

Mössbauer investigations between 4.5 and 300 K of iron minerals formed during the growth of the binary culture containing two anaerobic alkaliphilic bacteria-dissimilatory iron-reducing Geoalkalibacter ferrihydriticus (strain Z-0531) and organotrophic Anaerobacillus alkalilacustre (strain Z- 0521), have been carried out. Mannitol (2 g/l) as the sole substrate with amorphous Fe(III) hydroxide at final concentration 10 or 100 mM were added to the mineral medium. The formation of siderite and probable magnetite or a mixture of magnetite and maghemite were observed.