Thomas–Fermi–Dirac models of atoms constrained by nuclear cusp and long-range conditions

The traditional Thomas–Fermi–Dirac model of the electronic structure for a neutral atom is deficient in that it predicts an infinite electron density at the nucleus and a sharp cutoff of the electron density at a finite radius. This study was carried out to remedy these faults in the model. Extending an idea used earlier in Thomas–Fermi (TF ) theory [Proc. Natl. Acad. Sci. U.S.A. 83 , 3577 (1985)], the Thomas–Fermi–Dirac (TFD ) energy functional is minimized under constraints ∫ρ( r ) d r = N, ∫e^?2kr▽²ρ( r )d r < ∞ and ∫(1 ? e^?k′r)ρ^4/3( r )d r < ∞, with k and k′ determined by the nuclear cusp condition and the correct asymptotic behavior. Optimum coordinate scaling also is considered. It is found that the TFD model is substantially improved by constraining the minimization search domain of the energy functional in this way. Energies are given for five noble gas atoms, and Compton profiles for these atoms are calculated. The behavior of electrons in momentum space is improved in both this modified TFD model and in the corresponding modified TF model.     

A convergent approach to batzelladine alkaloids. Total syntheses of (+)-batzelladine E, (−)-dehydrobatzelladine C,and (+)-batzelladine K

We recently reported a convergent strategy to access the polycyclic guanidinium alkaloid (+)-batzelladine B via an aldol addition–retro-aldol–aza-Michael addition cascade. Here we describe the application of this approach toward the total syntheses of (+)-batzelladine E, (?)-dehydrobatzelladine C, and (+)-batzelladine K. The identification of suitable methods to functionalize a common tropane core by electrophilic alkynylation and nucleophilic 1,2-addition were essential to generalizing this approach. We provide evidence for the intermediacy of an acylallene species in the cascade reaction.     

Production of hair intercomparison materials for use in population monitoring programmes for mercury and methylmercury exposure

Ten kilograms of hair obtained from India were used as the basis for two intercomparison materials, one with natural low levels of mercury and methylmercury, and one with an elevated level of methylmercury. The latter was produced by labeling the hair with a solution containing methylmercury. To convert the hair into homogeneous powders, cryogenic milling was utilized. 70% of the final material passed through a 0.075 mm sieve. Subsequent studies were carried out to establish the homogeneity of the materials and the stability of the methylmercury label. The materials will be distributed in an international intercomparison, the results from which will be used to obtain recommended values for total mercury and methylmercury.     

Determination of minor and trace elements in Turkish diet by duplicate portion technique

The minor and trace element content of diet samples from two different social population groups were determined. Samples were prepared by duplicate portion technique by colecting everything 16 subjects ate and drank during a 3-day period. Samples were homogenized, freeze-dried and elemental concentrations of Br, Co, Cr, Cs, Fe, K, Na, Rb, Sc, Se and Zn were determined by instrumental neutron activation analysis. Elemental concentrations and daily dietary intake of the elements were compared with the diets of other nations.     

On the redistribution of electrons for chemical reaction systems

A regional density-functional theory is formulated and applied to the study of ground-state electron redistributions during the course of a chemical reaction. If for a given increment of the reaction process, accumulation of electrons occurs in a certain region of space, then it is called the dynamic acceptor region, denoted by P. The complement is called the dynamic donor region, denoted by Q. The regional energy itself is determined as a unique functional of the electron density of the total system. The regional transfer potentials are defined in such a way that they add to give the total chemical potential, and their values along the reaction coordinate are found to be different between P and Q. The difference between the regional transfer potentials is shown to provide the driving force for electron transfer from Q to P. A characteristic coordinate for following electron transfer and an associated excitation potential are introduced. The excitation potential is a measure of regional virtual excitation due to regional interactions. The regional transfer potential gives the local character of electron transferability, while the excitation potential gives the global character. The theory encompasses the concepts of regional hardness and softness and sheds light on the HSAB principle.     

Zur Bestimmung des Gesamt-Kohlenstoffs in Kohlen und Bodenarten

Ohne Zusammenfassung     

Complexity of chaotic binary sequence and precision of its numerical simulation

Numerical simulation is one of primary methods in which people study the property of chaotic systems. However, there is the effect of finite precision in all processors which can cause chaos to degenerate into a periodic function or a fixed point. If it is neglected the precision of a computer processor for the binary numerical calculations, the numerical simulation results may not be accurate due to the chaotic nature of the system under study. New and more accurate methods must be found. A quantitative computable method of sequence complexity evaluation is introduced in this paper. The effect of finite precision is evaluated from the viewpoint of sequence complexity. The simulation results show that the correlation function based on information entropy can effectively reflect the complexity of pseudorandom sequences generated by a chaotic system, and it is superior to the other measure methods based on entropy. The finite calculation precision of the processor has significant effect on the complexity of chaotic binary sequences generated by the Lorenz equation. The pseudorandom binary sequences with high complexity can be generated by a chaotic system as long as the suitable computational precision and quantification algorithm are selected and behave correctly. The new methodology helps to gain insight into systems that may exist in various application domains such as secure communications and spectrum management.     

Beyond electronegativity and local hardness: Higher-order equalization criteria for determination of a ground-state electron density

Higher-order global softnesses, local softnesses, and softness kernels are defined along with their hardness inverses. The local hardness equalization principle recently derived by the authors is extended to arbitrary order. The resulting hierarchy of equalization principles indicates that the electronegativity/chemical potential, local hardness, and local hyperhardnesses all are constant when evaluated for the ground-state electron density. The new equalization principles can be used to test whether a trial electron density is an accurate approximation to the true ground-state density and to discover molecules with desired reactive properties, as encapsulated by their chemical reactivity indicators.