Current trends in the computational modelling of polyoxometalates

Computational chemistry applied to the study of polyoxometalates has achieved its maturity in the last years. During two decades, important advances have been made using theoretical tools in the comprehension and interpretation of many relevant issues. In the present mini-review, we want to stress that different techniques have been incorporated to the routine of computation: from the very first Hartree?CFock LCAO-SCF calculation on the decavanadate anion, followed by numerous density functional theory?Cbased studies on increasingly complex systems, also applying correlated ab initio techniques for magnetism and, more recently, using molecular dynamics to analyse properties in liquid media, the information provided by computational chemistry gets more and more relevant.     

Theoretical study of the role of solvent Stark effect in electron transitions

The possible influence of the solvent Stark effect (SSE) on the solvatochromic shift in electron transitions has been analyzed by using the ASEP/MD (averaged solvent electrostatic potential from molecular dynamics) method. With this purpose, four molecules, two polar (acrolein and formaldehyde) and two non-polar (p-difluorobenzene and trans-difluoroethene) have been studied in solvents of diverse polarity. Independently of the nature of the system we found that the contribution of SSE on the average value of the solvent shift or on the multipole moment values is negligible. In the case of centro-symmetric molecules, our results permit to discard the SSE as cause of the solvent shift found, which must be assigned to the electrostatic interaction of the solute quadrupole and higher multipoles with the solvent. As the SSE values provide also a measure of the errors introduced by the mean field approximation (MFA), these results indicate that MFA permits a very accurate determination of the solvent shift at the same time that it reduces drastically the computational cost. Finally, a new procedure suited to the ASEP/MD method has been presented that permits to estimate the inhomogeneous broadening of spectral bands, complementing the information provided by mean field theories. This procedure does not need additional quantum calculations and its computational cost is minimal.     

Formal Verification of Numerical Programs: From C Annotated Programs to Mechanical Proofs

Numerical programs may require a high level of guarantee. This can be achieved by applying formal methods, such as machine-checked proofs. But these tools handle mathematical theorems while we are interested in C code, in which numerical computations are performed using floating-point arithmetic, whereas proof tools typically handle exact real arithmetic. To achieve this high level of confidence on C programs, we use a chain of tools: Frama-C, its Jessie plugin, Why and provers among Coq, Gappa, Alt-Ergo, CVC3 and Z3. This approach requires the C program to be annotated: each function must be precisely specified, and we prove the correctness of the program by proving both that it meets its specifications and that no runtime error may occur. The purpose of this paper is to illustrate, on various examples, the features of this approach.     

M?ssbauer analysis of high-energy mechanical-milled sand fraction of a magnetic soil developing on basalt

A sample of the coarse sand fraction from the soil material of the A-horizon (0?C0.2 m from the soil surface) of a dusky red magnetic Oxisol was submitted to high-energy mechanical milling for different times. This assay aimed mainly at (a) monitoring the individualization of strongly aggregated mineral particles, and (b) measuring the effect of the milling pressure on the mineralogy changes of the material. These data are also intended to experimentally subside any physical model describing the mechanical behavior of the superficial soil layer that is subjected to intensive machine management, in agriculture fields. Powder X-ray data reveal that some mineralogical phases, notably gibbsite, disappear soon after the first few hours milling. The 298 K-transmission Mössbauer spectrum for the non-milled sand sample shows a qualitatively typical pattern for the sand fraction of basalt derived soils, with magnetically ordered sextets, assignable mainly to hematite and maghemite, and an intense central (super)paramagnetic Fe^3?+? doublet. For the milled samples, spectra revealed progressive spectral reduction of the magnetic hyperfine structure, with concomitant increase of relative subspectral areas due to (super)paramagnetic phases, as the milling time increased. This result is consistent with the reduction of measured saturation magnetization, from 4.96(8) J T^???1 kg^???1, for the non-milled sample, to 3.26(7) J T^???1 kg^???1, for the sample milled for 8 hours.     

聚变堆熔盐冷却偏滤器靶板结构设计与分析

为提高偏滤器的抗中子辐照能力,兼顾高热承载能力和聚变堆经济性的需要,提出了基于熔盐冷却(MSC)的偏滤器靶板结构设计。它采用FLiNaK作为冷却剂,钨镧合金为热沉材料,钨为第一壁材料。通过数值计算评估了靶板的热负荷承载能力,并完成了偏滤器冷却剂回路设计,优化了偏滤器各模块之间的流量分配。此MSC偏滤器靶板设计可以有效去除10~15MW•m^-2热负荷,为适应未来聚变堆偏滤器靶板发展的需要提供了一种设计解决方案。     

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在对国内外液态锂回路研究综述的基础上,重点介绍了四川大学流动液态锂回路的研究进展。为开展等离子体与流动自由液态锂表面相互作用的研究而设计了该回路,其目标是：(1)获得稳定、均匀的流动自由液态锂表面;(2)研究等离子体辐照下液态锂的蒸发、溅射以及氢、氢同位素和氦在液态锂中的滞留行为;(3)研究等离子体辐照下液态锂与结构材料的相容性。系统包括液态锂循环部分和直线高密度等离子体发生装置。     

Unimodularity of zeros of self-inversive polynomials

We generalise a necessary and sufficient condition given by Cohn for all the zeros of a self-inversive polynomial to be on the unit circle. Our theorem implies some sufficient conditions found by Lakatos, Losonczi and Schinzel. We apply our result to the study of a polynomial family closely related to Ramanujan polynomials, recently introduced by Gun, Murty and Rath, and studied by Murty, Smyth and Wang as well as by Lalín and Rogers. We prove that all polynomials in this family have their zeros on the unit circle, a result conjectured by Lalín and Rogers on computational evidence.     

Selective solid phase extraction of platinum on an ion imprinted polymers for its electrothermal atomic absorption spectrometric determination in environmental samples

An ion-imprinted polymer (IIP) was obtained by copolymerization of methacrylic acid (as a functional monomer) and ethylene glycol dimethacrylate (as a crosslinking agent) in the presence of various chelators for Pt(II) ion and using 2,2??-azo-bis-isobutyronitrile as the initiator. Specifically, acetaldehyde thiosemicarbazone (AcTSn) and benzaldehyde thiosemicarbazone (BnTSn) were used as chelators. The IIPs were applied as sorbents for solid-phase extraction of Pt(II) and Pt(IV) ions from aqueous solutions. The effects of acidity and flow rate of the sample, of elution conditions and of potentially interfering ions were investigated. The imprinting effect of analyte is clearly demonstrated by the fact that only the IIP is capable of quantitative retention of Pt(II) and Pt(IV) ions. The method works best in the pH range from 0.5 to 1 and from 3.5 to 9.5. The ions can be recovered with an acidic solution of thiourea. The Pt-AcTSn polymer displays better sorption properties for the separation of analytes. The selectivity coefficients of the Pt-AcTSn and control polymers for Pt(IV) in the presence Pd(II), Rh(III), Ru(III), Al(III) and Cu(II) were calculated, and the sorbent capacity for Pt(IV) was found to be 4.56???g?g?^-1. The method was successfully applied to the determination of Pt(IV) by electrothermal atomic absorption spectrometry in tap water, tunnel dust and anode slime samples.

A certified reference material for radionuclides in the water sample from Irish Sea (IAEA-443)

A new certified reference material (CRM) for radionuclides in sea water from the Irish sea (IAEA-443) is described and the results of the certification process are presented. Ten radionuclides (³H, ⁴⁰K, ⁹⁰Sr, ¹³⁷Cs, ²³⁴U, ²³⁵U, ²³⁸U, ²³⁸Pu, ^239+240Pu and ²⁴¹Am) have been certified, and information values on massic activities with 95% confidence intervals are given for four radionuclides (²³⁰Th, ²³²Th, ²³⁹Pu and ²⁴⁰Pu). Results for less frequently reported radionuclides (⁹⁹Tc, ²²⁸Th, ²³⁷Np and ²⁴¹Pu) are also reported. The CRM can be used for quality assurance/quality control of the analysis of radionuclides in water samples, for the development and validation of analytical methods and for training purposes. The material is available in 5 L units from IAEA (http://nucleus.iaea.org/rpst/index.htm).