Kinetic Approach to the Interpretation of Analyte Losses During the Preatomization Thermal Treatment in Electrothermal Atomization Atomic Absorption Spectrometry

A method for evaluating E_a(loss), the apparent activation energy of the analyte loss process during the high-temperature thermal pretreatment stage in electrothermal atomization atomic absorption spectrometry (ETA-AAS) has been developed. The method is based on extracting information from the declining portion of thermal pretreatment curves (in this case presented as absorbance vs pyrolysis time at various fixed temperatures). Five volatile analytes (As, Pb, Sb, Se, and Sn) have been studied in the presence of tungsten chemical modifier (20 μg of W in H₂O₂).

The data on E_a (loss) have been utilized together with those obtained from treating the atomization peaks E_a and with literature data on known values of bond energies and enthalpies of certain chemical reactions. Possible mechanisms of analyte losses and atomization are discussed.     

不同掺杂的钇系-123薄膜磁通特性

我们在磁场中分别测量了最佳掺杂的YBa2Cu3O7-δ、钙0．2掺杂的Y1-xCaxBa2Cu3O7-δ及钙0．5掺杂的Pr1-xCaxBa2Cu3O7-δ薄膜的电阻温度关系．利用最近Zhang et al.[Phys．Rev．B71（2005），052502]提出的热激活能的分析方法对薄膜的磁通特性进行了分析、比较与讨论．     

A MINDO/3 MO study of oxidized flavins

The use of semi-empirical molecular orbital methods for the study of biologically important molecules has increased in recent years. The validity of well-known approximate Hartree-Fock molecular orbital methods such as MINDO/3 and MNDO still remains largely untested for biological molecules. Here we report its first application to the study of the electronic structures of isoalloxazines. Electronic charge distribution, variation of dipole moment, first ionization potential, electron affinity, orbital energies and electronic transitions are examined. Some of these results are compared with experiments. Good correlations with experiments were generally found in net atomic charge distributions, ionization potentials and electronic transitions. As a result of relatively good correlations with experiment application of the MINDO/3 method for extended study of biologically important coenzymes is promising.     

On impacts with friction

For modeling contacts or more specifically impacts we have two possible concepts. Either we discretize the contact zone by applying some continuum mechanical approach, or we use a rigid body model, where the impact behavior follows from complementarity rules. It depends on the problem itself, which approach might be more convenient, more contact details in the first and more system aspects in the second case. In the following we shall consider the second method and apply it to large industrial problems.     

Analytical computation of amplification of coupling in relativistic equations with Yukawa potential

The approximate analytic solutions to the Klein-Gordon and Dirac equations with the Yukawa potential were derived by using the quasilinearization method (QLM). The accurate analytic expressions for the ground state energies and wave functions were presented. These high-precision approximate analytic representations are obtained by first casting the proper relativistic equation into a nonlinear Riccati form and then solving that nonlinear equation in the first QLM iteration. The choice of zero iteration is based on general features of the exact solutions near the origin and infinity. To estimate the accuracy of the QLM solutions, the exact numerical solutions were found, as well. The analytical QLM solutions are found to be extremely accurate for a small exponent parameter w of the Yukawa potential. The reasonable accuracy is kept for the medium values of w. When w approaches the critical values, the precision of the QLM results falls down markedly. However, the approximate analytic QLM solution to the Dirac equation corresponding to the maximum relativistic effect turned out to be very accurate even for w close to the exact critical , whereas the QLM calculations yield . This effect of “amplification” in compare with the Schrödinger equation critical parameter was investigated earlier [S. De Leo, P. Rotelli, Phys. Rev. D 69 (2004) 034006]. In this work, it was found that the “amplification” for the Klein-Gordon equation became all the more evident. The exact numerical value is , whereas the QLM approximation yields .     

Phase diagram of a two-dimensional electron system

The melting curve of the two-dimensional electron system is interpolated between the known classical and ground state limits. The coexistence curve encloses a finite solid-phase domain, as in the three-dimensional case.     

The structures of some trimers of carbon monoxide—An infrared matrix isolation spectroscopic and ab initio molecular orbital study

Using a number of potential models for the gas-phase structure of the trimer of carbon monoxide as a guide, ab initio molecular orbital calculations have been carried out on this aggregate in order to determine its probable structure and vibrational spectrum in cryogenic matrices. The Fourier transform infrared spectra of carbon monoxide trapped in argon and nitrogen matrices have been recorded and, on the basis of the results of the theoretical calculations, a search for possible absorptions which may be assigned to trimeric species has been undertaken.     

Chiral induction in photochemical reactions. 14. : Linear free energy relationships as an instrument for the prediction of either de values or conformation energies of the auxiliary in the diastereoselective Paternò-Büchi reaction.

To value a stoichometric asymmetric synthesis it is important for a synthetic chemist to gain information about those structural elements of a chiral auxiliary which are responsible for high diastertomeric excesses in a particular reaction. Furtheron it is desirable to have detailed knowledge about the mechanism of the chirality transfer. In this paper an empirical relation is formulated for the correlation of structural variations of a chiral auxiliary and its influence of the diastereomeric excess in the photochemical oxetane formation in correspondance to the Ugi/Ruch concept. For this purpose we use a Linear Free Energy Relationship (LFER) which we have adjusted to reaction (2) in order to obtain quantitative information about the selectivity of this reaction on the basis of special parameters of the auxiliary applied.     

Atomic and molecular energies as functionals of the electrostatic potential

Starting from the Hohenberg–Kohn theorem, atomic and molecular energies have been expressed rigorously as functionals of the electronic electrostatic potential, V_elec(r). Explicit formulations have been derived for the functionals representing the kinetic energy and electronic interaction contributions to the total energies.Acknowledgements. The assistance of Dr. Jane S. Murray is greatly appreciated.Contribution to the Jacopo Tomasi Honorary Issue     

Quasi-SU(3) truncation scheme for even–even sd-shell nuclei

The quasi-SU(3) symmetry was uncovered in full pf and sdg shell-model calculations for both even–even and odd–even nuclei. It manifests itself through a dominance of single-particle and quadrupole–quadrupole terms in a Hamiltonian used to describe well-deformed nuclei. A practical consequence of the quasi-SU(3) symmetry is an efficient basis truncation scheme. In [C.E. Vargas et al., Phys. Rev. C 58 (1998) 1488] it is shown that when this type of Hamiltonian is diagonalized in an SU(3) basis, only a few irreducible representations (irreps) of SU(3) are needed to describe the yrast band, the leading S=0 irrep augmented with the leading S=1 irreps in the proton and neutron subspaces. In the present article the quasi-SU(3) truncation scheme is used, in conjunction with a “realistic but schematic” Hamiltonian that includes the most important multipole terms, to describe the energy spectra and B(E2) transition strengths of ^20,22Ne, ²⁴Mg and ²⁸Si. The effect of the size of the Hilbert space on both sets of observables is discussed, as well as the structure of the yrast band and the importance of the various terms in the Hamiltonian. The limitations of the model are explicitly discussed.