Quantum-Chemical Study of the Profiles of Reactions that Form Pyrrole Anion N-Adducts with CS<Subscript>2</Subscript> and CO<Subscript>2</Subscript>

The profiles of reactions leading to pyrrole anion N-adducts with CO₂ and CS₂ have been studied by the ab initio (RHF/6-31+G*, MP2/6-31+G*) and density functional (B3LYP/6-31+G*) methods. Addition of the pyrrole anion to the carbon disulfide molecule is accompanied by the appearance of a minimum corresponding to a pre-reaction complex. The transformation of the complex to the N-pyrrolyldithiocarboxylate anion occurs via a low activation barrier, which is due to repolarization of the C=S bonds. The profile of the reaction leading to the pyrrole anion N-adduct with CO₂ does not contain any intermediate stationary points throughout the whole route from reagents to products.Original Russian Text Copyright © 2004 by V. B. Kobychev, N. M. Vitkovskaya, I. L. Zaitseva, and B. A. Trofimov__________Translated from Zhurnal Strukturnoi Khimii, Vol. 45, No. 6, pp. 990–993, November–December, 2004.     

Coherent quantum transport in normal-metal/d-wave superconductor/normal-metal double tunnel junctions

Taking into account the effects of quantum interference and interface scattering, combining the electron current with hole current contribution to tunnel current,we study the coherent quantum transport in normal-metal/d-wave superconductor/normal-metal (NM/d-wave SC/NM) double tunnel junctions by using extended Blonder-Tinkham-Klapwijk (BTK) approach. It is shown that all quasiparticle transport coefficients and conductance spectrum exhibit oscillating behavior with the energy, in which periodic vanishing of Andreev reflection (AR) above superconducting gap is found.In tunnel limit for the interface scattering strength taken very large, there are a series of bound states of quasiparticles formed in SC.     

Low energy properties of identical and strongly correlated particles

Interesting qualitative consequences can arise from the quantum mechanical identity among strongly correlated particles that carry spin. This is demonstrated for properties connected with the low energy excitations in molecular and electronic systems. Spatial permutations among the identical particles are used as the key features. The particular behaviour of rotational tunneling molecules or molecular parts under the influence of dissipation are discussed together with the consequences arising for conversion transitions. The relationship between the thermal shifting of the tunneling line and the conversion rate at low and at elevated temperatures is explicated. The valuable information, that can be extracted from the conversion behaviour after isotopical substitution, is explained in detail. At low temperatures qualitative changes are predicted for the conversion rate by deuteration. Weakly hindered rotors show, also experimentally, drastic isotopic effects. The second part is devoted to finite systems of strongly interacting electrons that appear in semi-conductor nano-structures. The lowest excitation energies are strongly influenced by the interaction. They can be understood and determined starting from the limit of crystallized electrons by introducing localized many particle ‘pocket states’. The energy levels show multiplet structure, in agreement with numerical results. The total electron spin, associated with the low energy excitations, is crucially important for the nonlinear transport properties through quantum dots. It allows for instance to explain the appearance of negative differential conductances.     

Characterization of heat-assisted magnetic probe recording on CoNi/Pt multilayers

A method of heat-assisted magnetic recording (HAMR) potentially suitable for probe-based storage systems is characterized. In this work, field emission current from a scanning tunneling microscope (STM) tip is used as the heating source. Pulse voltages of 2–7 V were applied to a CoNi/Pt multilayered film fabricated on either bare silicon or oxidized silicon substrates. Different types of Ir/Pt and W STM tips were used in the experiment. The results show that thermally recorded magnetic marks are formed with a nearly uniform mark size of 170 nm on the film fabricated on bare silicon substrate when the pulse voltage is above a threshold voltage. The mark size becomes 260 nm when they are written on the identical film fabricated on an oxidized silicon substrate. The threshold voltage depends on the material work function of the tip, with W having a threshold voltage about 1 V lower than Pt. A synthesized model, which contains the calculation of the emission current, the simulation of heat transfer during heating, and the study of magnetic domain formation, was introduced to explain experimental results. The simulation agrees well with the experiments.     

Mechanism of the thermal decomposition of nitrates from graphite furnace mass spectrometry studies

A basically new mechanism of the thermal decomposition of solids is proposed to explain the mass spectral observations of gaseous molecules of CoO, CuO, Cu₂O, NiO, PbO and Mg(OH)₂ during the low-temperature decomposition of the anhydrous and hydrated nitrates of these metals. The mechanism consists of two stages: congruent gasification of all reaction products irrespective of their saturated vapor pressure and subsequent condensation of the low-volatility species (oxides and hydroxides). The partial pressures of these species at the appearance temperatures calculated from this theory for the first stage of the process (1–50 mPa) are in agreement with the detection limits of the quadrupole mass spectrometers used in these experiments. The proposed mechanism is supported by other available data obtained by thermal analysis.     

Short-range order and F ion diffusion inside the Pb1 − xAlxF2 + x solid solution Part II: Al NMR investigation and proposal of clustering process

A ²⁷Al nuclear magnetic resonance (NMR) investigation at room temperature of the Pb_{1 − x}Al_xF_{2 + x} (0 ≤ x ≤ 0.12) solid solution and of the ordered Pb₉Al₂F₂₄ phase is carried out. Two different types of aluminium ions are identified and their ratio is determined as a function of x. A clustering process based on the formation of column clusters, more and more extended when x increases, is proposed on the basis of results issued from the ¹⁹F (Part I) and ²⁷Al NMR investigations.     

Ge_x Si_(1-x)/Si超晶格中纵声学声子的喇曼散射强度研究

本文用光弹理论,在全面考虑了超晶格中两种材料的声速,质量密度和光弹常数存在差别的基础上,计算了Ge_xSi_(1-x)/Si超晶格中折迭纵声学声子的喇曼散射强度,在高达50cm~(-1)的频率范围内,理论值和实验符合得很好。     

铽－甲基吲哚乙酰丙酮三元配合物发光过程研究

测定和分析了ＲＥ．Ｌ１．Ｌ２（ＲＥ＝Ｔｂ（Ⅲ）、Ｇｄ（Ⅲ），Ｌ１＝３Ｍ（３甲基吲哚－１－乙酰基丙酮），Ｌ２＝ＴＰＰＯ、Ｐｈｅｎ、Ｄｉｐｙ）三元配合物的荧光光谱、磷光光谱、磷光寿命及变温荧光光谱等．讨论了Ｔｂ（Ⅲ）与配体之间的能级匹配和Ｌ１与Ｌ２的三重态之间传能的问题，说明了影响这些三元配合物荧光效率的主要因素及其发光过程．     

Nitroxyl free radical binding to Si(1 0 0): a combined scanning tunneling microscopy and computational modeling study

The ultra-high vacuum scanning tunneling microscope (UHV-STM) was used to investigate the addition of the 2,2,6,6-tetramethyl-1-piperidinyloxy (TEMPO) radical to the Si(1 0 0) surface. Room temperature studies performed on clean Si(1 0 0)-2 × 1 confirm the proposed binding of the unpaired valence electron associated with the singly occupied molecular orbital (SOMO) of the molecule with a Si dangling bond. A strong bias dependence in the topography of isolated molecules was observed in the range of −2.0 to +2.5 V. Semiempirical and density functional calculations of TEMPO bound to a three-dimer silicon cluster model yield occupied state density isosurfaces below the highest occupied (HOMO) and unoccupied state densities isosurfaces above the lowest unoccupied molecular orbital (LUMO) which trend in qualitative agreement with the bias dependent STM topography. Furthermore, the placement of TEMPO molecules on dangling bonds was controlled with atomic precision on the monohydride Si(1 0 0) surface via electron stimulated desorption of H, demonstrating the compatibility of nitroxyl free radical binding chemistries with nanopatterning techniques such as feedback controlled lithography.     

H andH NMR Relaxation in Hydrogen-Bonded Solids Due to a Complex Motion: Classical Jumps over a Barrier and Incoherent Tunneling

Equations for the temperature dependence of proton and deuteron spin–lattice relaxation rates and second moments due to a complex motion consisting of classical jumps over a potential barrier and quantum mechanical tunneling through the barrier have been derived. Asymmetric double and triple potential wells are considered. These equations have been employed to analyze proton spin–lattice relaxation data for solid naphthazarin in the laboratory and rotating frames as a function of temperature. It is shown that tunneling plays an important role in the proton transfer dynamics of this compound.