Heat of formation of solid solution of alkali halides

Based on a semicontinuum model, the electrostatic, the polarisation, and the repulsive energy change of a lattice is calculated numerically, as a function of the relaxation of the nearest neighbouring ions of a substitutional impurity in an alkali halide crystal. It is found that for a particular displacement, the total energy change of the lattice is a minimum. Thus the heat of formation of a dilute solid solution is obtained. Here, we report calculations on the heat of formation of the following systems-Na⁺ in LiCl, Li⁺ in NaCl, K⁺ in NaCl, Na⁺ in KCl, Rb⁺ in NaCl, Na⁺ in RbCl, F^? in NaCl, Cl^? in NaF. Br^? in NaCl and Cl^? in NaBr.     

A solid-state NMR study of the formation of molecular sieve SAPO-34

This work examined the formation of a catalytically important microporous material, SAPO-34, in the presence of HF under hydrothermal synthesis conditions. The local environments of P, Al, F and Si atoms in several solid phases obtained at different stages of crystallization were characterized by several solid-state NMR techniques including ³¹P, ²⁷Al, ¹⁹F and ²⁹Si MAS, ²⁷Al triple-quantum MAS, ³¹P{²⁷Al} transfer of populations in double-resonance, ²⁷Al{³¹P} rotational-echo double-resonance (REDOR), ²⁷Al→³¹P heteronuclear correlation spectroscopy, ³¹P{¹⁹F} and ²⁷Al{¹⁹F} REDOR as well as ¹H→³¹P cross polarization. The NMR results provide the new insights into the formation of SAPO-34.     

Effect of residual atmospheric pressure on the development of electrostatic discharges at the surface of protective glasses of solar cells

Electrostatic discharges obtained upon the irradiation of K-208 glass with 40-keV electrons at a flux density φ of 10¹⁰ to 2 × 10¹¹ cm^–2 s^–1 are studied. The residual pressure p _v in the vacuum chamber is varied from 5 × 10^–5 to 5 × 10^–3 Pa. Structural changes in the sample surfaces are studied by atomic-force microscopy. Depending on the pressure level, two types of discharges are observed in experiments at 3 × 10¹⁰ ≤ φ ≤ 1.2 × 10¹¹ cm^–2 s^–1: a microprojection at the glass–ionized-residual-atmosphere surface and a discharge which develops along the irradiated surface. It is found that at 5 × 10^–5 ≤ p _v ≤ 3 × 10^–4 Pa and 8 × 10¹⁰ ≤ φ ≤ 10¹¹ cm^–2 s^–1, discharges of the first type appear at the beginning of exposure; that is, an increase in microprojections is observed. Further, surface discharges propagate through these microprojections. At 10^–3 ≤ p _v ≤ 5 × 10^–3 Pa and 10¹⁰ ≤ φ ≤ 5 × 10¹⁰ cm^–2 s^–1, on the contrary, discharges of the second type are realized at the beginning. These discharges result in the appearance of channels with inhomogeneities on the glass, at which subsequently discharges of the first type occur. It is determined by calculations that in the region adjacent to the exposed glass surface, secondary electrons accelerated in a field of charge accumulated in the glass make the main contribution to the ionization of gases.     

Calculation of conformations and vibrational spectra of a monomeric fragment of the 2,6-carboxymethyl cellulose molecule

A theoretical conformational analysis has been carried out for the side substituents of a fragment of the molecule for 2,6-carboxymethyl cellulose (a water-soluble cellulose ether), and the frequencies and the potential energy distribution of the normal vibrations have been calculated for the most stable conformers of the ether groups of this fragment in the approximation of the molecular mechanics method. It has been shown that the most stable conformers are those that have the conformations gg, t, g⁻, g⁻, g⁻-for the groups of atoms on the bonds C5-C6, C6-O6, C13-O6, C10-C13, C10-O9 and the conformations g⁺g⁻, g⁺, g⁻, g⁻; g⁺g⁻, g⁻, g⁻, g⁻; g⁺g⁻, g⁻, g⁺, t for the groups of atoms on the bonds C2-O2, C11-O2, C7-C11, C7-O8. Comparative analysis of the calculated frequencies and the potential energy distribution of the normal vibrations for 13 of the most stable conformers showed, as in the case of the 2,6-hydroxyethyl cellulose molecule, that the frequencies and modes of the normal vibrations are highly sensitive to conformational transitions in the analyzed spectral region (800–1500 cm⁻¹). The characteristic patterns for the change in the frequencies and modes of the normal vibrations have been established in connection with conformational transitions within both side substituents. The observed conformational lability of the bulky substituents in the cellulose ether molecules and its manifestations in the vibrational spectrum provide a basis for hypothesizing that one of the major mechanisms for the process of their thermal gelation in aqueous solutions is conformational transitions within these substituents. __________ Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 74, No. 1, pp. 5–15, January–February, 2007.     

Theoretical study of low lying electronic states of GdO

Low lying electronic states of GdO have been investigated by complete active space SCF (CASSCF) and multireference singly and doubly excited configuration interaction (MRSDCI) calculations using the model core potential (MCP) method. The 4f electrons of Gd were included explicitly in the valence space. Relativistic effects were incorporated in the MCP and basis sets for Gd at the level of Cowan and Griffin's quasirelativistic Hartree—Fock method. The ⁹Σ^? state (f⁷σ) was the ground state, and excited states, ⁹Δ, ⁹Π, 2⁹Σ^?, ⁷Σ^?, ⁷Δ, ⁷Π, and 2⁷E^?, lay between 0 ～ 22 300 cm^?1. The energy separations for these states agreed well with available experimental values. Calculated GdO bond lengths and vibrational frequencies for these states are in the ranges of 1.81–1.85 Å and of 800–880 cm^?1, respectively. Mulliken population analysis showed that the gross population of the 4f orbitals was 7.1 e for all these states, and that the 4f electrons were strongly localized on Gd atom. The effective charge distribution was approximated to be Gd⁺O^?. The σ and π bonding orbitals were mainly formed by Gd 5d and O 2p orbitals.     

Lifetime measurements of excited levels in prompt fission products of 252Cf

Lifetimes in the range 10⁻¹¹ to 10⁻⁹ s of prompt γ rays emitted from the fission fragments of ²⁵²Cf were measured using a recoil distance method. A ²⁵²Cf source was deposited on a stretched Ni foil and placed in a plunger device, the recoil direction of the studied fragments being determined by the detection of the complementary fragment. The lifetime was determined by the change in the non-Doppler-shifted peak intensities of prompt γ rays as a function of the source-plunger distance. The 2⁺ → 0⁺ half-life in ¹¹²Pd and 4⁺ → 0⁺ halflives in ^{104, 106}Mo, ^108,110Ru and ¹⁴²Ba were determined for the first time. Several other measurements of longer lived 2⁺ → 0⁺ transitions were repeated as well. The experimental results are discussed within the framework of the rotational and the IBA-2 models.     

Observation of phase transition of cesium manganese hexacyanoferrates by X-ray absorption spectroscopy

Cesium manganese hexacyanoferrates exhibit an interesting phenomenon of temperature-induced phase transition accompanied by a variation in the magnetic susceptibility. We observed the variation in the electronic state of Mn during the phase transition by using X-ray absorption spectroscopy. The results of the analyses showed that the content ratio of Fe^II-CN-Mn^III and Fe^III-CN-Mn^II systematically varied during the phase transition. However, the ratio of Fe^II-CN-Mn^II remained constant at almost all temperatures. These results suggest that the charge transfer between Fe and Mn ions in the Fe^III-CN-Mn^II or the Fe^II-CN-Mn^III bond produces the phase transition.     

About the limits of existence of α-cluster structure in nuclei

The shape of the d-α coincidence spectrum from the reaction ¹²C(⁶Li, d)¹⁶O(α)¹²C in the region corresponding to the 20.9 MeV 7^? level in ¹⁶O has been measured. Also, measurements of the α-particle elastic scattering excitation functions on ¹²C and ¹⁶O have been made in the regions corresponding to the α-cluster levels found in the (⁶Li, d) reactions. A comparison of the d-α coincidence spectra and excitation functions allows us to draw conclusions about splitting of the α-cluster states and region of their existence.     

The effects of ion implantation on the anodic oxidation of silicon

The effects of H⁺, C⁺, N⁺, Ne⁺, Al⁺, P⁺, Cl⁺, Ar⁺, Ga⁺, As⁺, Kr⁺, Sb⁺, Xe⁺, Au⁺ and Tl⁺ ion implantation on the anodic oxidation of Si have been investigated as a function of dose and energy, in the as-implanted stage and after heat treatment at temperatures up to 1050°C. It is speculated that the location, in the formed oxide, of agglomerates containing the dopant, and the influence of these agglomerates on oxygen diffusion in SiO₂ and/or oxygen evaluation at the oxide/solution interface are factors which account for the enhancement/retardation of the anodic oxidation.     

Comparison of the Kinetics of the Exchange Mechanism of the Thallium Ion with 18C6 and with Pentaglyme in Acetonitrile Solutions

Abstract

In acetonitrile solutions, the exchange reaction is bimolecular in the Tl⁺ + 18C6 system, while in the Tl⁺ + pentaglyme system the associative-dissociative and the bimolecular mechanisms coexist at room temperature and the bimolecular exchange reaction dominates at 263° K. For the bimolecular mechanism in the case of Tl⁺ + 18C6 and the associative-dissociative mechanism in the case of Tl⁺ + pentaglyme, the activation energies of the exchange reactions change with temperature. At 298° K, in the Tl⁺ + 18C6 system the activation energy for the bimolecular exchange reaction is ≈ 2 kcal.mol^?1 and exchange rate constant (k₁) is (4.1 ± 0.1) × 10⁷ s^?1mol^?1; in the Tl⁺ + pentaglyme system, the activation energy for the associative-dissociative exchange reaction is ≈ 5 kcal mol^?1 and the decomplexation rate constant (k_?2) is (2.2 ± 0.4) X 10⁵ s^?1. The activation energy for the bimolecular exchange in the Tl⁺ + pentaglyme system was determined to be 3.00 ± 0.05 kcal.mol_?1 and the exchange rate constant (3.0 ± 0.1) X 10⁸ s^?1 mol^?1.     

Rotational Spectroscopy of HBS: The Quadrupole Coupling Constant of S in Thioborine

The unstable HBS molecule has been produced in the gas phase by a high-temperature reaction between crystalline boron and hydrogen sulfide. Ground state rotational spectra have been observed in the millimeter-wave region, from 75 to 460 GHz, for the previously unobserved H¹¹B³³S and H¹⁰B³³S isotopic species. The analysis of the hyperfine structure produced by the ^10/11B and ³³S nuclear spins in the low-J rotational transitions has yielded the first evaluation of the quadrupole coupling constant of 33S in the thioborine molecule, which was 6.361(15) MHz in H¹¹B³³S and 6.329(17) MHz in H¹⁰B³³S. In addition, further measurements have been performed for the most abundant isotopomers H^10/11B^32/34S, for which improved values of rotational, centrifugal, and hyperfine structure constants have been determined.     

Readjustment of the Bohr stopping force from energies of keV/n to a few tens of MeV/n ions in elemental targets

An analytical approach for the electronic stopping force for non-relativistic energies that has no adjustable parameters has been developed. The approach combines the Bohr model for the close collisions and the Firsov model for the distant collisions. In order to combine the two models, a probabilistic model was introduced. We have applied our model to ¹⁶O in ¹²C, ¹⁶O in ²⁷Al, ⁸⁴ Kr in ²⁷Al, ⁵Li in ¹²C, ¹²C in ¹²C, and ¹³²Xe in ¹²C systems and compared with SRIM/MSTAR software, the original Bohr model, the Firsov model and available experimental data. We have found that the calculated electronic stopping force values are in agreement with the general qualitative behaviour of the electronic stopping force as a function of particle velocity reported in the literature. The proposed analytical formula is expected to be valid for other projectile-target combinations but more experimental data are needed to verify this assumption.     

Characterization of adsorption mode of new B2 bradykinin receptor antagonists onto colloidal Ag substrate

In this paper, the surface‐enhanced Raman scattering (SERS) spectra of the potent B₂ bradykinin receptor antagonists, [D‐Arg⁰,Hyp³,Thi^5,8,L‐Pip⁷]BK, Aaa[D‐Arg⁰,Hyp³,Thi^5,8,L‐Pip⁷]BK, [D‐Arg⁰,Hyp³,Thi⁵,D‐Phe⁷,L‐Pip⁸]BK, and Aaa[D‐Arg⁰,Hyp³,Thi⁵,D‐Phe⁷,L‐Pip⁸]BK, were measured when immobilized onto a colloidal assembly of apparently randomly adhering Ag spheres with diameters of approximately 20 – 25 nm. The observed SERS bands corresponding to different vibrational modes of the molecule, attached to or near Ag, and the variations in these bands resulting from competitive interactions of the functional groups of the peptides with the SERS‐active Ag surfaces were analyzed in this study. Briefly, it was shown that Pip, in generally in vertical orientation, and Thi, in the edge‐on position, relative to the colloidal Ag surface interacted with this surface through their lone electron pairs on the nitrogen and sulfur atoms, respectively. The imide bond of the X‐Pro peptide linkage and the guanidine group of Arg were involved in the adsorption process. In addition, it was demonstrated that the specific differences in the amino acid sequences slightly influenced the mode of adsorption. For example, Aaa in Aaa[D‐Arg⁰,Hyp³,Thi^5,8,L‐Pip⁷]BK and Aaa[D‐Arg⁰,Hyp³,Thi⁵,D‐Phe⁷,L‐Pip⁸]BK and D‐Phe (vertical with respect to the colloidal Ag surface) in [D‐Arg⁰,Hyp³,Thi⁵,D‐Phe⁷,L‐Pip⁸]BK, and Aaa[D‐Arg⁰,Hyp³,Thi⁵,D‐Phe⁷,L‐Pip⁸]BK assisted in the adsorption of these peptides onto the colloidal Ag particles. To discuss these spectral alterations due to the different surface adsorption mechanisms of these peptides, the spectral changes were analyzed according to the adsorption process and Fourier‐transform‐Raman spectra. Copyright © 2013 John Wiley & Sons, Ltd.     

Vibrational Structure of the B—X System of Isotopic Ago Molecules

Spectra of ¹⁰⁷Ag¹⁸O and ¹⁰⁷Ag¹⁶O molecules have been obtained in a low-pressure arc in oxygen atmosphere, and recorded with medium dispersion. Vibrational assignments for the bands of B ²π —X²π system were verified by the study of the oxygen isotope effect, and the vibrational constants were obtained for the states involved in transitions.     

The role of OH ions in the stabilization of F colour centres in LiF

Thermally Stimulated Depolarisation Current (TSDC) and optical methods are applied to a range of alkali-fluoride crystals in order to establish a model for the stable F ₂ ⁺ - like colour centres in LiF:OH^-. The experimental results for LiF:OH^- suggest that the OH^- defects are partially destroyed under ionising irradiation or during crystal growth. The low-temperature dielectric relaxation signals in LiF:OH^- and LiF:Mg²⁺,OH^- are attributed to highly interacting hydroxide ions and products of their destruction located in extended lattice defects. In LiF:OH^-, in contrast to other alkali halides, the results advocate for a defect-structure model, which considers a neutral defect (ND, probably O₂ or H₂) sited at the anion vacancy of the O^2--V _a ⁺ dipole and which possibly is the “nucleus” for the F ₂ ⁺ centre. The proposed F ₂ ⁺ (ND, O^-) model seems to better explain the dielectric results, compared to the older F ₂ ⁺ (O^2-) and F ₂ ⁺ (O^-) models. The estimate for the electric dipole moment derived from the experimental TSDC bands, gives a value for the F ₂ ⁺ - like centre in LiF:OH^- between those of the F ₂ ⁺ (O^-) and F ₂ ⁺ (O^2-) defects, in good agreement with the proposed F ₂ ⁺ (ND,O^-) model. The reduction of the activation energy barrier of the (re)orientation process of the Mg²⁺V _c ^- (OH^-) complexes in LiF:Mg²⁺,OH^-, and the low-temperature shift of their TSDC band, compared to the single Mg ₂ ⁺ V _c ^- peak in LiF:Mg²⁺, are tentatively ascribed to an increase in the crystal-lattice parameters owing to the presence of OH^- and/or products of its destruction. Received 31 August 2001 / Received in final form 30 March 2002 Published online 9 July 2002     

Role of thermal and photobeta decays in processes of nucleosynthesis of problematic p nuclei of 113In, 115Sn, 92,94Mo, and 96,98Ru in massive stars

The temperature dependence of the rates of ¹¹³Cd →¹¹³In, ¹¹⁵In →¹¹⁵Sn, ⁹²Zr→⁹²Nb →⁹²Mo, ⁹⁴Zr→⁹⁴Nb →⁹⁴Mo, ⁹⁶Mo →⁹⁶Tc→⁹⁶Ru, and ⁹⁸Mo→⁹⁸Tc→⁹⁸Ru thermal beta transitions was studied at temperatures of massive-star matter in the range of 1 × 10⁸–6 × 10⁹ K. These decays are the possible channel of synthesis of the p nuclei of ¹¹³In, ¹¹⁵Sn, ⁹²,⁹⁴Mo, and ⁹⁶,⁹⁸Ru. The abundances of these nuclei present a challenge for models that study the explosivemechanism of synthesis. The contribution of photobeta decay to the synthesis of the aforementioned p nuclei was estimated. It was shown that the channel of thermal beta decay for ¹¹³In, ¹¹⁵Sn, ⁹⁴Mo, and ⁹⁸Ru p nuclei and the channel of photobeta decay for the ⁹⁶Mo p nucleus could be efficient at the high-temperature quasiequilibrium stage of massive-star evolution.     

Outer-Sphere Interaction in Hexafluorocomplexes of Elements of Group IV with Cations of Alkali Metals and Ammonium

IR-absorption spectra of M²AF⁶hexafluorocomplexes (M-Na, K, Rb, Cs and NH⁴; A=Si, Ge, Sn) were obtained and intergrated intensities of bands assigned to stretching vibrations of AF⁶ ions were measured. The reasons for the influence of exchange of the central atom and an outer-sphere cation on the intergrated intessities of vibration bands are discussed. It was found that the ammonium ion does not fit into the earlier established pattern of intensity dependence on cation size. Analysis of the frequencies v³ (AF⁶) suggeste that this is coused by the presence in (NH⁴)²AF⁶ of hydrogen bonds N-H F of different strength.

The question of the influence of anther-sphere cation on the spectral properties of complex compounds has been treated in the literature ^1-6. The dependence of vibrational frequencies characterizing the anion ^1-3, the integrated intensity vibration bands (IIVB) in IR-absorption spectra ⁴, chemical shiftn in ¹⁹ f NMR apectra ² and the luminescent properties of complexed on cation nature have been established.     

Dynamic SIMS ion microscopy imaging of individual bacterial cells for studies of isotopically labeled molecules

A CAMECA IMS-3f SIMS ion microscope instrument capable of 500 nm spatial resolution was used for imaging single bacterial cells in the soil treated with ¹³C-labeled phenol in desired treatments. After formaldehyde fixation, the soil samples containing bacterial cells were smeared on the silicon substrate. The O₂⁺ primary ion beam was used for the detection of negative secondary ions. Images of individual bacterial cells were recorded on a CCD camera in masses 24, 25, 26, and 27 signals. The respective mass images represented contributions from the molecular ions of interest, for example ²⁴(¹²C₂)⁻, ²⁵(¹³C¹²C)⁻, ²⁶(¹²C¹⁴N)⁻, ²⁷(¹³C¹⁴N)⁻, as well as interfering mass species associated with a particular mass. However, in cells treated with ¹³C-labeled phenol the enhancement of signals in masses 25 and 27 images due to increased signals of ²⁵(¹³C¹²C)⁻ and ²⁷(¹³C¹⁴N)⁻, respectively, unequivocally indicated the presence of ¹³C-labeled phenol in bacterial cells in direct comparison to the samples treated only with unlabeled phenol. The ratio images of masses 25/24 and 27/26 from individual cells revealed a cell-to-cell heterogeneity in the labeling with ¹³C-phenol. This study indicates that the ion microscope can be applied effectively for studies of labeled molecules in microbiology and biogeochemistry.     

Spin dependence of the shape of even-even nuclei within the Davydov-Chaban model

Within a model of a nonaxial even-even nucleus soft in β vibrations, the shape parameters of the ¹⁵⁴Gd, ^156,158,160Dy, ^164,168Er, ¹⁶⁸Yb, ¹⁷⁶Hf, and ¹⁸⁰W nuclei are calculated in the quadrupole approximation as functions of the excited-state spin.