Scattering of NO from a graphite surface at cryogenic temperatures

The scattering of NO molecules from a graphite surface at cryogenic temperatures (T_s<80 K) allows to study the molecular translation-rotation energy transfer without surface phonon contributions in the entrance channel. The angular distributions show that there are no diffusely scattered molecules at surface temperatures below T_s=70 K, whereas the signal of forward scattered molecules remains present down to T_s=20 K, the lowest temperature investigated. The rotational behavior of the scattered molecules can be described by a Boltzmann distribution characterized by a rotational temperature T_rot. It is nearly constant below T_s=80 K and is determined by the molecular kinetic energy in surface normal direction. The data are consistent with the formation of a short-lived collision complex (NO··C_n) between the NO molecule and a few surface atoms. The complex decomposes in a unimolecular fashion. The cryogenic surface temperatures require effective shielding of the crystal from the heat radiation of the surrounding experimental equipment. The data show that the heat radiation influences the crystal temperature, however, it has only negligible influence on the molecule–surface interaction.     

Electrical current pulsations through ion irradiated polymer foils in electrolytes

Funnel-type ion tracks were produced in thin polymer foils by swift heavy ion irradiation and subsequent treatment with both low concentration etchants and acids from two different sides. The funnel shapes consist of shallow etched cones and residual latent tracks and thus combine both their characteristic properties, rectification and current spike emission, in one track each. Arrays of spike-emitting tracks are known to exhibit phase-locked synchronous electrical pulsations in accordance with the neural network theory. These pulsations were studied here on arrays of funnel-type tracks for the first time. As expected, the results strongly depend on the track density. In foils with low track densities, synchronous oscillations are rare and rather unstable events, whereas foils with high track densities exhibit stable, strong and long-lasting pulsations. Insertion of 0.1 M KCl solution into tracks at low density improved the shape and regularity of the spuriously occurring spikes somewhat, as compared with water in these tracks.     

<Superscript>10</Superscript>B<Superscript>+</Superscript>-ion implantation into photoresist

100-keV ¹⁰B⁺ ions were implanted into photoresist in different directions at a fluence of 1×10¹⁴ cm^-2, and their depth distribution was determined by means of the neutron depth profiling technique. In no case were the projectile ions found to come to rest according to their predicted implantation profiles. Instead, they are always found to undergo considerable long-range migration. During the irradiation process this motion appears to be enhanced by the radiation damage, and during the subsequent annealing steps one deals with thermal diffusion. The implant redistribution is always found to be governed strongly by the self-created damage, insofar as both electronic and nuclear defects in the polymer act as trapping centers. The implant redistribution shows a pronounced directional dependence, essentially as a consequence of the spatial distribution of the electronic energy loss. The changes of the nuclear defect distribution during thermal annealing are studied by a specially developed tomographic method in three dimensions. PACS 61.72.Ww; 61.80.Jh; 61.41.+e; 66.30.-h; 66.30.Jt     

Towards a detailed understanding of the NEXAFS spectra of bulk polyethylene copolymers and related alkanes

High energy resolution C 1s near-edge X-ray absorption fine structure (NEXAFS) spectra of ethylene-1-alkene copolymers with systematic variations in comonomer content and thus systematic changes in branch length, branching ratio, and degree of crystallinity are presented. Spectral changes of the σ^*_C–H/Rydberg and σ^*_C–C features in these ideal model systems provide unambiguous experimental evidence for intermolecular interactions with profound effects on the spectral intensity, but only very small energy shifts. Ab initio calculations reproduce the experimental results in detail. The intermolecular interaction observed suggests that interpretation of NEXAFS spectra based on calculations of isolated molecules can be insufficient even in relatively weakly interacting macromolecules.     

b 1Σ+ Emissions from group V–VII diatomic molecules: bO+ → X1 O+ emission of Pl

Chemilluminescence of the bO⁺ → X₁O⁺ band system of P1 has been observed in a discharge flow system. Thirty-eight bands of the sequences, δν = +2, +1, 0, ?1, ?2 and ?3 were recorded photoelectrically at medium resolution. Evidence is presented that the vibrational numering assigned to the bands in the recently published first analysis of this system has to be modified. The re-analysis leads to the new constants (in cm ^?1) T_e = 11135 ± 5, ω′_e 400 ± 2, ω_e′_e = 1.4 ± 0.3, ω″_e = 372 ±2 and ωχ″_e, 1.4 ± 0.3 for the bO⁺ and χ₁ states, respectively. An upper limit of 0.01 was found for the ratio of the (0.0) band intensifies of the two sub-systems bO⁺ → χ₂ 1 and bO⁺ → χ₁O⁺.     

Half-life of the h9/2 shell-model intruder-state isomer Au

The half-life of the $\text{9}\text{2}{}^{\mathrm{?}}$ shell-model intruder-state isomer in ¹⁸⁷Au has been measured by employing a technique in which each incoming event is tagged with a digital representation of time by means of a real-time clock. With this method we obtain a 2.3 ± 0.1 sec half-life for the $\text{h}{}_{\mathrm{<mtext>9</mtext><mtext>2</mtext>}}\text{→}\text{d}{}_{\mathrm{<mtext>3</mtext><mtext>2</mtext>}}$ E3 isomeric transition resulting in a retardation of 50 relative to the Weisskopf single-particle estimate.     

Physikalische und physikochemische Mikromethoden und -apparate

Ohne Zusammenfassung     

Über Alkali-hexachlorochromate(III): Na3CrCl6

Alkali-hexachlorochromates(III): Na₃CrCl₆ X-ray investigations on single crystals yielded for Na₃CrCl₆ a trigonal structure: space group P3 1c; a = 682.0(3) pm; c = 1203.4(5) pm; Z = 2. In a hexagonal-close arrangement of Cl^? ions, 2/3 of the octahedral holes are occupied orderly by Na⁺ and Cr³⁺ ions. The Na compounds of V³⁺ and Mo³⁺ are isotypic. The chlorochromates with K and Rb are crystallizing with the K₃MoCl₆ structure according to X-ray photos of powders. The alkali metal ions habe the C.N. 8 or 11 related to the chloride ions. These compounds and elpasolithes A₂BCrCl₆ (A = Cs? K; B = Rb? Na) can be treated in the same way with the concept of tolerance factors as it is known for the chloro-perovskites AMCl₃. For all compounds the temperatures of phase transitions were determined by DTA. Some structures could be solved from high-temperature-Guinier-patterns, by comparing them with patterns of substances with known structures.     

Arsenvergiftungen

The development of legal verification from torture via post mortem examination to chemical and radiochemical detection methods is shown by means of some spectacular cases of arsenic poisoning from the 17^th to the 20^th century. Because of the omnipresence of arsenic, it was not always possible to resolve all doubts.