Quantum wave packet calculation of reaction probabilities,cross sections,and rate constants for H+ + LiH → Li + H reaction

The H⁺ + LiH → Li + H reactive scattering has been studied using a quantum real wave packet method. The state‐to‐state and state‐to‐all reaction probabilities for the entitled collision have been calculated at zero total angular momentum. The probabilities for J > 0 are estimated from the J = 0 results by using J‐shifting approximation based on the Capture model. The integral cross sections and thermal rate constants are then calculated. © 2006 Wiley Periodicals, Inc. Int J Quantum Chem, 2006     

Methods for the calculation of spherically averaged Compton profiles with GTOs

For the first time, an analytical and efficient algorithm for the evaluation of spherically averaged reciprocal form factors B(s)=〈B( s )〉_Ω using Gauss-type basis functions is presented. The spherically averaged Compton profile is available by Fourier transformation of the reciprocal form factor. The algorithm has been successfully implemented in connection with the quantum chemistry codes GAMESS and CRYSTAL92, which perform Hartree–Fock calculations for molecules and solids. In addition, an analytical algorithm for the direct evaluation of spherically averaged Compton profiles and the moments 〈p^ν〉 (ν≥−1) via the momentum density is proposed for Gauss-type basis functions. © 1997 John Wiley & Sons, Inc. Int J Quant Chem 65 : 213–223, 1997     

Modification in physical properties of organo clay filled polyurethane nanocomposites

Polyurethane (PU) have been prepared by using polyether polyol (jagropol oil) and 1,6-hexamethylene diisocyanate (HMDI) as a cross-linker. The organically modified montmorillonite clay (o-MMT) is well dispersed into urethane matrix by in-situ polymerization method. A series of PU/o-MMT nanocomposites have been prepared by varying amounts viz., 1, 3, 5 and 6 wt % of nanoclay. The mechanical properties such as tensile strength, percentage elongation at break and tensile modulus of the composites were experimentally determined. The swelling behavior of the composites has been studied in different organic solvents. It was noticed that the swelling data of the composites significantly depends on the solubility parameters of the solvents. Microcrystalline parameters such as, lattice strain (g in %), average number of unit cells (〈N〉) in direction perpendicular to Bragg plane, surface weighted crystal size (D _s) and interplanar distance (d _hkl ), were calculated from X-ray patterns. These parameters were computed using Exponential asymmetric column length distribution functions. Morphological features of cryofractured PU/o-MMT composites were also analyzed using scanning electron microscopy (SEM).     

Compton profiles and momentum space inequalities

Rigorous upper and lower bounds to the atomic Compton profileJ(q) are obtained for any value of the momentum transferredq in terms of radial expectation values 〈p ⁿ 〉 of the atomic momentum density γ(p). In doing so, a procedure based on moment-theoretic techniques and Chebyshev inequalities has been used. This type of results can be employed to study the compatibility of diverse information obtained by using different models, techniques, numerical calculations or experimental data. The same method allows also to obtain approximations to the Compton profile and to bound other relevant characteristics ofJ(q). A comparison of the approximations with some previously known Maximum Entropy Approximations is done. In order to test the accuracy of the bounds, a numerical study of the results is carried out in a Hartree-Fock framework for atomic systems.     

On the history of cluster beams

The methods to produce and investigate cluster beams have been developed primarily with the use of permanent gases. A summary is given of related work carried out at Marburg and Karlsruhe. The report deals with the effect of carrier gases on cluster beam production; ionization, electrical acceleration and magnetic deflection of cluster beams; the retarding potential mass spectrometry of cluster beams; cluster size measurement by atomic beam attenuation; reflection of cluster beams at solid surfaces; scattering properties of⁴He and³He clusters; the application of cluster beams in plasma physics, and the reduction of space charge problems by acceleration of cluster ions.     

Radiation induced defects on Si-SiO2 interface

The density of surface states at Si?SiO₂ interface is examined for dry and wet oxidization process on 〈111〉 silicon substrate. The trivalent silicon centers are probably responsible for thermal and radiation generated surface states at the Si?SiO₂ interface. The dependence of the radiation induced surface state density is compared for various oxide thicknesses and oxidization methods used.     

Covalence reduction factors of four-coordinated pseudo-tetrahedral paramagnetic compounds inD 2d symmetry

Theoretical expressions for the covalence reduction factors of orbital angular momentum and spin-orbit coupling in pseudo-tetrahedral four-coordinated paramagnetic complexes withD _2d symmetry, denoted ask's andR's respectively, have been derived. p ]The mixing coefficients in the antibonding MO's for the CuCl ₄ ^2- ion in three complexes are estimated using suitable approximations. It is shown thatk's must be less thanR's in Tinkham's approximation. Certain misconceptions existing in the literature regarding the value of the integral 〈p _u |???u|s〉 have been clarified.     

In Situ Characterization of Proteins Using Laserspray Ionization on a High-Performance MALDI-LTQ-Orbitrap Mass Spectrometer

The MALDI-LTQ-Orbitrap XL mass spectrometer is a high performance instrument capable of high resolution and accurate mass (HRAM) measurements. The maximum m/z of 4000 precludes the MALDI analysis of proteins without generating multiply charged ions. Herein, we present the study of HRAM laserspray ionization mass spectrometry (MS) with MS/MS and MS imaging capabilities using 2-nitrophloroglucinol (2-NPG) as matrix on a MALDI-LTQ-Orbitrap XL mass spectrometer. The optimized conditions for multiply charged ion production have been determined and applied to tissue profiling and imaging. Biomolecules as large as 15 kDa have been detected with up to five positive charges at 100 K mass resolution (at m/z 400). More importantly, MS/MS and protein identification on multiply charged precursor ions from both standards and tissue samples have been achieved for the first time with an intermediate-pressure source. The initial results reported in this study highlight potential utilities of laserspray ionization MS analysis for simultaneous in situ protein identification, visualization, and characterization from complex tissue samples on a commercially available HRAM MALDI MS system. Graphical Abstract

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Role of fragmentation processes in the liquid metal ion source production of aggregates

We analyse the role of the fragmentation processes in the liquid metal ion source technique from a theoretical and an experimental point of view. We show that the “double peak” structure of the energy distribution of Sn ₇ ⁺ ions is due to the fact that there are two kinds of ions. On the one hand, ions which are directly emitted from the tip; on the other hand, ions produced by fragmentation at some distance (100–1000 Å) from the tip. We show that the existence of a peak for the second kind of ions strongly depends on the electric field mapping. We also deduce from the energy separation of the two peaks a life-time of the mother particles. The value obtained is compared to an evaluation made with the RRKM theory. The charge and mass of the mother particles are also discussed.     

Structure of δ-Bi2O3 from density functional theory: A systematic crystallographic analysis

A systematic crystallographic analysis of the 〈110〉 and 〈111〉 vacancy-ordered structure of cubic δ-Bi₂O₃ obtained from electronic-structure calculations is presented. The ordering of vacancies leads to a doubling of the unit-cell that results in a 2×2×2 fluorite super-structure, with an associated reduction in its space group symmetry from to . The Bi atoms present inside the 〈111〉 vacancy-ordered oxygen sublattice have equal Bi-O bond lengths, whereas, those present inside the 〈110〉 vacancy-ordered oxygen sublattice have three different pairs of Bi-O bond lengths. The specific ionic displacements and electronic charge configurations also depend on the nature of vacancy ordering in the oxygen sub-lattice.     

The interaction of ruthenium with a MgO matrix

Ruthenium samples supported on MgO have been prepared and investigated by Thermal Programmed Reduction. Several TPR peaks have been observed and their assignment to chemical species containing reducible ions has been discussed.     

Theoretical studies of diamagnetic properties of the hydrogen molecule ion II. Effect of varying internuclear separation

The diamagnetic susceptibility χ and magnetic shielding σ for H are investigated in the range of internuclear separations R = 1.6 a.u. to R = 2.4 a.u. according to a previously reported technique. From this data values of 〈χ〉 and 〈σ〉, for which nuclear motion due to zero-point vibration and centrifugal stretching is taken into account, are calculated at 300°K. These averages are 〈χ〉 = ?0.3902 α²a and 〈σ〉 = 1.096 × 10^?5 c.g.s. units which are approximately 3.1% and 1.4% respectively, smaller than the equilibrium values.     

Light scattering study of an aromatic polyamide-hydrazide polymer

The aromatic Polyamide-hydrazide, Monsanto X-500, has been studied by light scattering in dimethyl sulfoxide, a thermodynamically good solvent. The unperturbed dimensions, (〈r〉_av/M)^1/2 = 1.93 × 10^?8 at 25°C., indicate a rather highly extended chain. The persistence length falls in the range 35–63 Å, which corresponds to a length of between two and four formula units. This is considerably smaller than the values which have been reported for the aromatic polyamides, poly(p-benzamide) and poly(p-phenylene terephthalamide). X-500 appears to approximate coil-like behavior at a molecular weight of 45,000. Theoretical predictions, based upon the 〈r〉_av/bL ratio, are compared with the observation that no evidence for an anisotropic phase has been found in X-500 solutions in dimethyl sulfoxide at polymer volume ranging from 0.12 to 0.19 (depending upon the concentration of added LiCl).     

Synthesis of network poly(N-vinylimidazole) and properties of the related hydrogels

Imidazole-containing network polymers have been prepared via quaternization of linear poly(1-vinylimidazole). Owing to the affinity for water, crosslinked poly(1-vinylimidazole) is capable of limited swelling in water and concomitant formation of polyelectrolyte hydrogels. Imidazole-containing hydrogels can be doped with different metal ions and can serve as matrixes for stabilization of particles obtained via reduction of nanosize metals.     

Application of solvation excess concept to solutions of 3 : 1 and 1 : 3 electrolytes

Data on water activity in solutions of a series of 3 : 1 and 1 : 3 electrolytes [AlCl₃, Al(NO₃)₃, LaCl₃, La(NO₃)₃, H₃PO₄, NaH₂PO₄] have been generalized in the frame of solvation excesses concept. Solvation excess reflects the distribution of the selected structural elements (ions or solvent particles) in the solution. The computed values have demonstrated the opposite contributions of ion association and hydration of ions and ion associates. Solvation excess concept allows determination of water molecules fraction constituting the excess at ions and their associates. The comparison of results obtained with different choice of model structural units has shown the electrolyte concentration ranges of validity of the respective models.     

All-electron calculations with plane waves in solid lithium hydride

Calculations of the directional Compton profiles and the anisotropies of Compton scattering are reported, based on the density functional theory in the local density approximation, performed in the plane-wave basis, and using full, unscreened Coulomb potentials for both Li and H atoms. It is shown that converged results can be obtained without employing pseudopotentials, and the Compton profiles obtained are in excellent agreement with experiment. The influence of correlation on Compton profiles in LiH is found to be very weak. Possibilities (and limits) of extending the plane-wave calculations with the full Coulomb potentials to other atoms and substances are discussed. © 1997 John Wiley & Sons, Inc.     

The Effect of O6+ and Si7+ ion beam irradiations on poly(lactide-co-glycolide) (50: 50) copolymer

Sterilization by ion beam radiations unfortunately also has a significant effect on the degradation of many polymers. The aim of present study is to examine the effect of heavy ion beam irradiation on poly(lactide-co-glycolide) (PLGA) (50: 50). The radiation effect is manifested through its degradation behavior and changes in the morphological, optical and structural properties. PLGA films are prepared by solvent casting method and subsequently irradiated with swift heavy ions O⁶⁺ and Si⁷⁺ ion with fluence in the range of 5 × 10¹⁰?1 × 10¹² ions/cm². The dominant effect on PLGA films is chain scission as evidenced by change in surface modification. Changes in optical and structural properties were analyzed by UV-Vis, XRD and FTIR spectrometric techniques. XRD technique is not responsive to degradation occurring in samples. Surface modifications caused by ion irradiations have been observed with SEM.     

Two-dimensional analysis of the SAXS of partially oriented polymers*)

The Small-angle X-ray scattering (SAXS) patterns of oriented LDPE (λ=1...5.7) were fitted by calculating the small-angle intensity for a structure consisting of a linear paracrystalline lattice built up by finite lamellar or cylindrical crystallites. The resulting data of the superstructure were compared with corresponding values from wideangle X-ray scattering. It is shown that it is impossible to get quantitative information about the superstructure of oriented polymers by using SAXS alone. Nevertheless, the qualitative transition of the crystals during orientation can be explained very well.     

Combining Ion Mobility Spectrometry with Hydrogen-Deuterium Exchange and Top-Down MS for Peptide Ion Structure Analysis

The gas-phase conformations of electrosprayed ions of the model peptide KKDDDDIIKIIK have been examined by ion mobility spectrometry (IMS) and hydrogen deuterium exchange (HDX)-tandem mass spectrometry (MS/MS) techniques. [M+4H]⁴⁺ ions exhibit two conformers with collision cross sections of 418 Ų and 471 Ų. [M+3H]³⁺ ions exhibit a predominant conformer with a collision cross section of 340 Ų as well as an unresolved conformer (shoulder) with a collision cross section of ~367 Ų. Maximum HDX levels for the more compact [M+4H]⁴⁺ ions and the compact and partially-folded [M+3H]³⁺ ions are ~12.9, ~15.5, and ~14.9, respectively. Ion structures obtained from molecular dynamics simulations (MDS) suggest that this ordering of HDX level results from increased charge-site/exchange-site density for the more compact ions of lower charge. Additionally, a new model that includes two distance calculations (charge site to carbonyl group and carbonyl group to exchange site) for the computer-generated structures is shown to better correlate to the experimentally determined per-residue deuterium uptake. Future comparisons of IMS-HDX-MS data with structures obtained from MDS are discussed with respect to novel experiments that will reveal the HDX rates of individual residues. Graphical Abstract

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Small-angle x-ray scattering from solution of rodlike particles with length distribution

The scattering function of rods with a constant radius, 8 Å, and a length distribution of the Schulz–Zimm type was calculated on a computer as a model of helical synthetic polypeptide. The influence of length and length distribution on the scattered intensity of small-angle x-ray scattering was clarified. As length grows and length distribution broadens it is difficult to obtain reliable values of molecular weight and radius of gyration from a Zimm plot. The influence of length distribution on the mass per unit length, M_q, and the radius of gyration of the cross section, 〈S〉^1/2, from the Guinier plot of the cross-sectional factor decreases as the length increases, and reliable values of M_q and 〈S〉^1/2 can be obtained even for rods with wide distribution for rods more than 600 Å long. In particular, it is pointed out that the value of 〈S〉^1/2 is little influenced by length and length distribution.