Higher-order <Emphasis Type="Bold">?</Emphasis> corrections in the semiclassical quantization of chaotic billiards

In the periodic orbit quantization of physical systems, usually only the leading-order ? contribution to the density of states is considered. Therefore, by construction, the eigenvalues following from semiclassical trace formulae generally agree with the exact quantum ones only to lowest order of ?. In different theoretical work the trace formulae have been extended to higher orders of ?. The problem remains, however, how to actually calculate eigenvalues from the extended trace formulae since, even with ? corrections included, the periodic orbit sums still do not converge in the physical domain. For lowest-order semiclassical trace formulae the convergence problem can be elegantly, and universally, circumvented by application of the technique of harmonic inversion. In this paper we show how, for general scaling chaotic systems, also higher-order ? corrections to the Gutzwiller formula can be included in the harmonic inversion scheme, and demonstrate that corrected semiclassical eigenvalues can be calculated despite the convergence problem. The method is applied to the open three-disk scattering system, as a prototype of a chaotic system. Received 10 September 2001 and Received in final form 3 January 2002     

Hydrogenic Rydberg atoms in strong magnetic fields: Theoretical and experimental spectra in the transition region from regularity to irregularity

For deuterium Rydberg atoms in a magnetic field of ～6 T we compare the complete experimental spectrum in the range ?190 cm^?1 to ?20 cm^?1 with the positions and oscillator strengths of the corresponding quantum theoretically calculated photoabsorption lines. The agreement is excellent. The range of energy covered extends from the end of thel-mixing regime up to the regions where the approximate integrability of the problem is completely lost, and the corresponding classical system undergoes a transition to chaos.     

Digests or extracts?—Some interesting but conflicting results for three widely differing polluted sediment samples

Three sets of samples have been investigated in some detail. One set is from a river polluted by mine workings, containing substantial levels of Fe, Mn,Cu, Zn and Ni with traces of many other metals. The second set consists of typical estuarine sediments contaminated from a wide range of industrial sources, and the third set consists of oily drilling cuttings from the sea bottom in the vicinity of a North Sea oil production platform.These samples have been subjected to treatment 1) with EDTA at two different pH's (extracts) 2) with HNO₃/H₂O₂ 3) with HNO₃/HCl and 4) with HNO₃/HCl/HF (digests). EDTA recoveries, compared toaqua regia digests, are often very reproducible, not dependent on pH, and usually significantly low. Nitric/peroxide andaqua regia digests often give very close results suggesting that these are meaningful values indicating the maximum levels of polluting metals in the sediments. However, the triple acid digest with HF does sometimes give higher values (and reasonable agreement for CRM's such as MESS-1) but with poorer reproducibility.     

Determination of metal ions by liquid chromatographic separation of their 2-acetylpyridine-4-ethyl-3-thiosemicarbazone chelates

A new thiosemicarbazone was prepared, characterized, and used as a complexing reagent for the chromatographic separation and determination of metal complexes by reverse-phase HPLC. The reagent was sufficiently soluble in methanol-water solutions for metal ions to be complexed in this aqueous organic phase, without need for extraction. Many variables affected the retention times of the metal complexes. Several metals were determined selectively by complexation with the reagent and chromatographic separation of the complexes. Interference effects from other metal ions were also investigated.     

The preparation of a new "safety catch" ester linker for solid-phase synthesis

A new "safety catch" linker for esters has been synthesized on polystyrene resin. This 2-tert-butoxyphenol resin 10 may be acylated to give a relatively stable ester that will allow nucleophilic chemistry without reaction at the linking ester group. Removal of the tert-butyl group with acid unmasks a highly reactive 2-hydroxyphenyl ester that reacts readily with nucleophiles to cause release of the product from the resin. This sequence has been exemplified by acylating the resin with various bromo acids, carrying out nucleophilic displacements with thiols, phenols, or amines, activating the ester with trifluoroacetic acid and cleaving from the resin with amines to give the (nucleophile) substituted carboxamides in high yield and purity. Kinetic studies with a model ester revealed half-lives for reaction with morpholine of 119 h for the tert-butoxyphenyl ester and 1 min for the corresponding phenol.     

以硫醚为主链的螯合树脂研究Ⅳ．含硫代硫酸根、叠氮基树脂的合成及吸附性能

聚环硫氯丙烷或环硫氯丙烷与环氧氯丙烷共聚物，在少量二乙烯三胺存在下制得交联预聚物，将交联预聚物分别与硫代硫酸钠，叠氮化钠反应，制得四种侧链带有硫代硫酸根或叠氮基的新型螯合树脂。它们对贵金属离子具有较高的吸附容量和较好的吸附选择性。