Die Verbesserung einer Methode zur experimentellen Bestimmung von Übergangswahrscheinlichkeiten und ihre Anwendung auf das Spektrum des Barium

The intensities of spectral lines emitted by an axialsymmetric light-source and transformed by the Abel-integral-equation are given as a function of the distance from the axis. If the local temperature is known and the emission will be reduced to the radiation of the black body, one can find out the probabilities of the transition. The method is applied to the spectrum of Barium in the region between 4000 and 7000 Å.     

Nondestructive analysis of single rapeseeds by means of Raman spectroscopy

The value of different vegetable oils can be correlated with the content of polyunsaturated fatty acids, especially omega‐3‐fatty acids such as linolenic acid, because of their contribution to healthy nutrition. One expression for the degree of unsaturation is the iodine value normally measured with gas chromatography. The use of Raman spectroscopy allows a rapid calculation of the iodine value and, in addition, only in a minimal sample volume. Therefore, this method can be used in single rapeseeds in order to predict the iodine value before harvesting. Additionally, the method can also be used for breeding investigations. Here, the lipid content and composition of a plant can be predicted by measuring the seedling without destruction. Copyright © 2006 John Wiley & Sons, Ltd.     

Depth profiling with SNMS and SIMS of Zn(O,S) buffer layers for Cu(In,Ga)Se2 thin‐film solar cells

Zn(O,S) is a promising candidate to replace the commonly used CdS buffer layer for Cu(In,Ga)Se₂ (CIGS) thin‐film solar cells due to its non‐toxicity and its potential to enhance the conversion efficiency of the CIGS solar cell. The composition of chemical bath deposited (CBD) and sputtered Zn(O,S) layers with thicknesses well below 100 nm was determined by sputtered neutral and secondary ion mass spectrometry (SNMS and SIMS). Despite numerous mass interferences of double‐charged atoms and dimers with single Zn, O and S isotopes, we developed an evaluation algorithm for quantification of SNMS depth profiles of Zn(O,S) layers. In particular, the superposition of double‐charged S and Zn atoms with O and S isotopes is accounted for numerically in the quantification procedure. For sputtered Zn(O,S) layers, the S/(S + O) atomic ratio and the vertical composition profile can be controlled by the O₂ content in the gas flow and the substrate temperature during sputtering whereas for CBD Zn(O,S) the S/(S + O) ratio is constant around 0.7–0.8. A Cu‐depleted layer of about 5 nm on the CIGS surface after buffer deposition was observed for both preparation methods. With negative SIMS, we found more hydroxides and carbon residues in CBD Zn(O,S) as compared to sputtered layers. Best cell performance with sputtered Zn(O,S) layers was achieved for S/(S + O) ratios of 0.25–0.40, yielding efficiencies up to 13%. Our solar cells with CBD Zn(O,S) buffers exhibit higher efficiencies due to an improved open‐circuit voltage. Copyright © 2013 John Wiley & Sons, Ltd.     

Kinetik der Konformations?nderung w?hrend der Mizellbildung in apolaren Medien

Ohne Zusammenfassung     

Is water critical to the formation of micelles in apolar media??

Photon correlation studies in H₂O/sodium di-2-ethylhexylsulfosuccinate (AOT)/i-C₈H₁₈-systems, pertinent IR. investigations, and vapor pressure osmometric measurements with alkylated quaternary ammonium di-2-ethylhexylsulfosuccinates strongly suggest water to be pre-requistite for the micellization in apolar media.     

Trends in the reactions of gaseous phenyl pnictogen radical cations C6H5EH2*+ (E = N, P, As)

In context of an analysis of the effect of the central atom E of gaseous radical cations of phenyl pnictogens C(6)H(5)EH(2), E = N (1), P (2), and As (3), the mass spectrometric reactions of phenyl phosphane 2 have been re-investigated by D-labeling and by using methods of tandem mass spectrometry. The 70 eV mass spectrum of 2 shows the base peak for ion [M-2H](*+) and significant peaks for ions [M-H](+), [M-(2C,3H)](+), [M-PH] (*+), and [M-(C,P,2H)](+). Metastable 2(*+) fragments exclusively by loss of H(2), and the investigation of deuterated 2-d(2) shows that excessive H/D migrations occur before fragmentation. Other significant fragment ions in the mass spectrum of 2 arise by losses of C(2)H(2,) P, or HCP from the ion [M-H](+). This mass spectrometric behavior puts the radical cation 2(*+) in between the fragmentation reactions of aniline radical cation 1(*+) (loss of H and subsequent losses of C(2)H(2,) or HCN) and phenyl arsane radical cation 3(*+) (elimination of H(2) and loss of As from ion [M-H](+)). The fragmentation mechanisms of the radical cations 1(*+) -3(*+) and of related ions were analyzed by calculations of the enthalpy of relevant species at the stationary points of the minimum enthalpy reaction pathways using the DFT hybrid functionals UBHLYP/6-311+G(2d,p)//UBHLYP/6-311+G(d). The results show that, in contrast to ionized aniline 1(*+), the reactions of the derivatives 2(*+) and 3(*+) of the heavier main group elements P and As are characterized by an easy elimination of H(2)via a reductive elimination of group C(6)H(5)-E (E = P, As) and by a special stability of bicyclic isomers of 2(*+) and 3(*+). Thus, while 1(*+) rearranges by ring expansion and formation an 7-aza-tropylium cation by loss of H., the increased stability of bicyclic intermediates in the rearrangement of 2(*+) and in particular of 3(*+) results in separate rearrangement pathways. The origin of these effects is the more extended and diffuse nature of the 3p and 4p AO of P and As.     

First regioselective cyclometalation reactions of cobalt in arylketones: C-H versus C-F activation

Phenyl ketones react smoothly under mild conditions with low valent cobalt(i) adducts to form new and stable five-membered cobaltacycles via C-H and C-F activation.