KMgF3:Ni2+晶体的占位、局部结构、吸收光谱和顺磁g因子的统一解释

利用完全对角化方法和强场耦合方案,采用半自洽场(semi-SCF)自由Ni2+的d轨道模型和Ni2+-6X-(x=F,Cl,Br,I)络合物的μ-κ-α模型研究,建立了含有过渡族金属离子的晶体的局域结构与吸收光谱和顺磁g因子之间的定量关系,对KMgF3:Ni2+晶体的占位、局域结构、吸收光谱和顺磁g因子作出了统一解释,预测了KMgF3:Ni2+晶体的光谱精细结构.所得理论计算结果与实验值符合得很好.     

The cavities in a random close-packed structure

The cavities in the random close packing of spheres are re-examined with a view to considering the possible applicability of the structure as a model for the arrangement of oxygen atoms in a silicate melt. For this purpose a limit of 1.20 diameters is used to define near contacts between spheres, and this leads to substantial changes in both the numbers and the types of polyhedral cavities found. Serious limitations are deduced for the Si: O ratios of silicate structures for which the random close packing might serve directly as a model, but suggestions are made as to how the introduction of ionic charges might itself tend to modify the packing into a more appropriate form.     

Ein neuer Apparat zur volumetrischen Kohlenstoffbestimmung

Ohne Zusammenfassung     

Quantum cascade laser-based free space optical communications

The advent of the quantum cascade laser (QCL) with emission wavelengths available in the infrared range from 3 μm through more than 100 μm opens up the possibility of exploiting infrared atmospheric transparency windows for free space optical communications. In an effort to establish the efficacy of using directly modulated QCLs for free space communications we have conducted a series of investigations that demonstrate the potential advantages of this technology. In these experiments we first establish that the QCL has very high modulation bandwidth. We then implement a practical free space communications link that under conditions of atmospheric fog, dust and other obscurants offers significant transparency advantage when compared with near infrared wavelength sources presently used in commercial free space optical communications links.     

The NMR spectra and conformations of cyclic compounds: IX—conformational studies of bicyclo(3,1,0)hexane derivatives by 13C NMR

The ¹³C spectra of α-thujene ( 1 ), isothujone ( 2 ), (?)isothujol ( 3 ), (+)neoisothujol ( 4 ), sabinol ( 5 ), dihydroumbellulone ( 6 ) and umbellulone ( 7 ) and the alcohol acetates are recorded and assigned. The C-6 chemical shift may be used in conjunction with the steric shift mechanism as a conformational probe in these molecules. The results obtained indicate that isothujol, neoisothujol, isothujone and dihydroumbellulone adopt boat-like conformations whilst sabinol has a much flatter conformation. Conjugation of the isolated double bond of α-thujene and the carbonyl group of dihydroumbellulone with the cyclopropane ring has virtually no effect on the ¹³C shifts, but those of umbellulone itself are anomalous, indicating conjugation of the α,β unsaturated ketone system with the cyclopropyl ring.     

Asymmetric lithiation-substitution of amines involving rearrangement of borates

Asymmetric lithiation of substituted benzylamines, N-Boc-pyrrolidine, or N-Boc-indoline using Beak's methodology was followed by electrophilic quench with trialkylboranes. The resulting borate intermediates rearrange with concomitant C-N bond breakage to give, after oxidation, chiral secondary alcohols with high enantioselectivity.     

Post-functionalization of ATRP polymers using both thiol/ene and thiol/disulfide exchange chemistry

In this communication, we report on a new route to the functionalization of ATRP polymers exploiting their halide end-groups, which were converted successfully into reactive disulfide end-groups, using sodium methanethiosulfonate. The resultant disulfide-terminated polymers could then be reacted with different functional thiols to yield functional polymers exploiting either thiol/disulfide exchange chemistry or thiol/ene "click" reactions.     

Synthesis of hindered anilines: copper-catalyzed electrophilic amination of aryl boronic esters

No longer a hindrance: copper-catalyzed electrophilic amination of aryl boronic esters is accomplished under mild reaction conditions using 2.5-5.0 mol % of a catalyst derived from copper tert-butoxide and Xantphos ligand. The reaction tolerates a wide range of functional groups and can be used to prepare some of the most hindered anilines made to date.     

Efficient identification of independence networks using mutual information

Conditional independence graphs are now widely applied in science and industry to display interactions between large numbers of variables. However, the computational load of structure identification grows with the number of nodes in the network and the sample size. A tailored version of the PC algorithm is proposed which is based on mutual information tests with a specified testing order, combined with false negative reduction and false positive control. It is found to be competitive with current structure identification methodologies for both estimation accuracy and computational speed and outperforms these in large scale scenarios. The methodology is also shown to approximate dense networks. The comparisons are made on standard benchmarking data sets and an anonymized large scale real life example.