Stereochemical analysis of ferrocene and the uncertainty of fluorescence XAFS data

Methods for the quantification of statistically valid measures of the uncertainties associated with X‐ray absorption fine structure (XAFS) data obtained from dilute solutions using fluorescence measurements are developed. Experimental data obtained from 10 mM solutions of the organometallic compound ferrocene, Fe(C₅H₅)₂, are analysed within this framework and, following correction for various electronic and geometrical factors, give robust estimates of the standard errors of the individual measurements. The reliability of the refinement statistics of standard current XAFS structure approaches that do not include propagation of experimental uncertainties to assess subtle structural distortions is assessed in terms of refinements obtained for the staggered and eclipsed conformations of the C₅H₅ rings of ferrocene. Standard approaches (XFIT, IFEFFIT) give refinement statistics that appear to show strong, but opposite, preferences for the different conformations. Incorporation of experimental uncertainties into an IFEFFIT‐like analysis yield refinement statistics for the staggered and eclipsed forms of ferrocene which show a far more realistic preference for the eclipsed form which accurately reflects the reliability of the analysis. Moreover, the more strongly founded estimates of the refined parameter uncertainties allow more direct comparison with those obtained by other techniques. These XAFS‐based estimates of the bond distances have accuracies comparable with those obtained using single‐crystal diffraction techniques and are superior in terms of their use in comparisons of experimental and computed structures.     

Angle of incidence effects in a molecular solid

We investigate the influence of the angle of incidence on the sputter yield when bombarding molecular solid, benzene, with C₆₀. Our simulations show that at normal incidence, essentially all of the projectile energy is deposited into the substrate within ∼2.5 nm of the surface. However, at 75° incident angle, only 35% of the projectile energy is deposited within a depth of less than 1.5 nm of the surface while 65% of the projectile energy is reflected. Therefore, important aspects of the collision process which are dependent upon energy deposition, such as sputter yield, ejection depth, and molecule dissociation, may change as the incident angle changes.     

Nowcasting Avalanches as Earthquakes and the Predictability of Strong Avalanches in the Olami-Feder-Christensen Model

Nowcasting earthquakes, suggested recently as a method to estimate the state of a fault and hence the seismic risk, is based on the concept of natural time. Here, we generalize nowcasting to a prediction method the merits of which are evaluated by means of the receiver operating characteristics. This new prediction method is applied to a simple (toy) model for the waiting (natural) time of the stronger earthquakes, real seismicity, and the Olami-Feder-Christensen earthquake model with interesting results revealing acceptable to excellent or even outstanding performance.     

The real geometry of complex space-times

This paper describes the geometry of complex space-times from the real point of view and presents some miscellane ous results on the existence and nature of real slices.     

Evidence for Anderson localisation in Landau level tails from the analysis of two-dimensional Shubnikov—de Haas conductivity minima

The amplitudes of the Shubnikov—de Haas conductivity minima are analysed for n-type inversion layers in Si 〈100〉 MOS devices. Thermal excitation between adjacent Landau levels, conduction through extended tail states and activated conduction from localised tail states are all detected in different magnetic field and temperature ranges. The minimum metallic conductivity found for the lowest spin extremum agrees well with theory but the values for higher Landau levels are lower than expected.     

Peptide structural analysis using continuous Ar cluster and C60 ion beams

A novel application of time-of-flight secondary ion mass spectrometry (ToF-SIMS) with continuous Ar cluster beams to peptide analysis was investigated. In order to evaluate peptide structures, it is necessary to detect fragment ions related to multiple neighbouring amino acid residues. It is, however, difficult to detect these using conventional ToF-SIMS primary ion beams such as Bi cluster beams. Recently, C₆₀ and Ar cluster ion beams have been introduced to ToF-SIMS as primary ion beams and are expected to generate larger secondary ions than conventional ones. In this study, two sets of model peptides have been studied: (des-Tyr)-Leu-enkephalin and (des-Tyr)-Met-enkephalin (molecular weights are approximately 400 Da), and [Asn¹ Val⁵]-angiotensin II and [Val⁵]-angiotensin I (molecular weights are approximately 1,000 Da) in order to evaluate the usefulness of the large cluster ion beams for peptide structural analysis. As a result, by using the Ar cluster beams, peptide molecular ions and large fragment ions, which are not easily detected using conventional ToF-SIMS primary ion beams such as Bi₃ ⁺, are clearly detected. Since the large fragment ions indicating amino acid sequences of the peptides are detected by the large cluster beams, it is suggested that the Ar cluster and C₆₀ ion beams are useful for peptide structural analysis.     

Catalytic Cleavage of Ether CO Bonds by Pincer Iridium Complexes

The development of efficient catalytic methods to cleave the relatively unreactive C? O bonds of ethers remains an important challenge in catalysis. Building on our group’s recent work, we report the dehydroaryloxylation of aryl alkyl ethers using pincer iridium catalysts. This method represents a rare fully atom‐economical method for ether C? O bond cleavage.     

捕获离子测试基本粒子物理学

科学无法解释,宇宙大爆炸后物质是如何产生的。所有已知的物理过程都留给我们一个物质和反物质基本等量的宇宙,那么为什么现实中一切都是由物质构成的呢？这个宇宙重子不对称(BAU)是现代物理学所面对的最大谜团,也是粒子物理前沿全方位攻坚之驱动力。最近,美国实验室天体物理联合研究所(JILA)由Eric Cornell 领导的研究组,利用桌面实验系统探索了这一前沿(采用捕获的分子离子探寻基本对称性的破坏)。研究人员特别寻找“电子电偶极矩”(eEDM)的迹象：他们没有发现痕迹,从而证实了以前实验的正确结论。