New interpretations of XPS spectra of nickel metal and oxides

A current interpretation of XPS spectra of Ni metal assumes that the main 6 eV satellite is due to a two hole c3d⁹4s² (c is a core hole) final state effect. We report REELS observation in AES at low voltages of losses (plasmons and inter-band transitions) corresponding to the satellite structures in Ni metal 2p spectra. The satellite near 6 eV is attributed to a predominant surface plasmon loss. A current interpretation of Ni 2p spectra of oxides and other compounds is based on charge transfer assignments of the main peak at 854.6 eV and the broad satellite centred at around 861 eV to the cd⁹L and the unscreened cd⁸ final-state configurations, respectively (L is a ligand hole). Multiplet splittings have been shown to be necessary for assignment of Fe 2p and Cr 2p spectral profiles and chemical states. The assignments of Ni 2p states are re-examined with intra-atomic multiplet envelopes applied to Ni(OH)₂, NiOOH and NiO spectra. It is shown that the free ion multiplet envelopes for Ni²⁺ and Ni³⁺ simulate the main line and satellite structures for Ni(OH)₂ and NiOOH. Fitting the NiO Ni 2p spectral profile is not as straightforward as the hydroxide and oxyhydroxide. It may involve contributions from inter-atomic, non-local electronic coupling and screening effects with multiplet structures significantly different from the free ions as found for MnO. A scheme for fitting these spectra using multiplet envelopes is proposed.     

Correlated and non-correlated growth kinetics of pentacene in the sub-monolayer regime

We present a study of the growth kinetics of pentacene monolayer islands on SiO₂ in the submonolayer regime by using Atomic Force Microscopy (AFM). Two distinct growth modes, namely correlated growth (CG) and non-correlated growth (NCG), have been identified by Voronoi tesselation. These two modes are characterized by different island growth kinetics. In the case of correlated growth, the average island size 〈A〉 scales with deposition time t i.e. 〈A〉 ∝ t whereas for non-correlated growth, 〈A〉 ∝ t². The CG and NCG regimes are defined by the level of re-evaporation which determines the capture zones around the islands: Wigner-Seitz cells for CG and coronas of width λ_D (λ_D is the mean diffusion distance on SiO₂ before re-evaporation) for NCG. A simple model is proposed to reproduce the experimental growth kinetics in both modes.     

Studies on pre-hump and main fractions of cellulose-2,5-acetate in acetone

Technical cellulose-2.5-acetates (CA 2.5) were characterized regarding their carbohydrate composition in comparison to the raw material. The association of the CA 2.5 samples in acetone was studied by size exclusion chromatography (SEC) using various acetone grades and styrene divinylbenzene copolymer columns. In HPLC grade acetone with and without addition of 1% water up to three different pre-humps eluted in front of the main fraction of the polymer. The evaluation of the main peak by light scattering measurements resulted in high molar masses indicating that for these technical CA 2.5 samples even the main fraction is not dissolved without association. No pre-humps or association phenomena were observed after addition of 1 ppm LiBr to HPLC grade acetone or with p.a. grade acetone. In addition pre-hump enriched and pre-hump free fractions were isolated by fractionated precipitation. The carbohydrate composition of these fractions was determined and correlated with their association pattern in SEC investigations.     

The effect of microscopic features upon the transmissivity of enclosed laser ablated laminated metallised polymer films

A vacuum-deposited aluminium layer (20 nm) is sandwiched between two layers of laminated oriented polypropylene (OPP) film whose thickness varies from 20 to 40 μm. Selected areas of this sealed system were transparentised by the redistribution of the aluminium layer without breaking the seal or causing damage to the OPP film using a 75 W Q-switched Nd:YAG laser. The resultant transparentised films contain aluminium particles, distorted polymer areas and intact areas of the vacuum-coated aluminium layer. This paper investigates the effect of microscopic features upon the overall transmissivity of the laser-treated films and hence the quality of the transparentisation process.     

Indecomposable modules over the Virasoro Lie algebra and a conjecture of V. Kac

We consider a class of indecomposable modules over the Virasoro Lie algebra that we call bounded admissible modules. We get results concerning the center and the dimensions of the weight spaces. We prove that these modules always contain a submodule with one-dimensional weight spaces. From this follows the proof of a conjecture of V. Kac concerning the classification of simple admissible modules.Preprint Université de Bourgogne-mai 1990     

Atomistic packing models for experimentally investigated swelling states induced by CO2 in glassy polysulfone and poly(ether sulfone)

Atomistic packing models have been created, which help to better understand the experimentally observed swelling behavior of glassy polysulfone and poly (ether sulfone), under CO₂ gas pressures up to 50 bar at 308 K. The experimental characterization includes the measurement of the time‐dependent volume dilation of the polymer samples after a pressure step and the determination of the corresponding gas concentrations by gravimetric gas‐sorption measurements. The models obtained by force‐field‐based molecular mechanics and molecular dynamics methods allow a detailed atomistic analysis of representative swelling states of polymer/gas systems, with respect to the dilation of the matrix. Also, changes of free volume distribution and backbone mobility are accessible. The behavior of gas molecules in unswollen and swollen polymer matrices is characterized in terms of sorption, diffusion, and plasticization. © 2006 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 44: 1874–1897, 2006     

Photodecomposition of several compounds commonly used as sunscreen agents

The photolysis reactions of three compounds commonly used as a sunscreen agents, Parsol 1789 (1-[4-(1,1-dimethylethyl)phenyl]-3-(4-methoxyphenyl)-1,3- propanedione), Oxybenzone ((2-hydroxy-4-methoxyphenyl)phenyl-methanone) and Padimate O (2-ethylhexyl-4-(dimethylamino)benzoate), were investigated to provide a chemical background to aid in the understanding of the photosensitization of the sunscreen agents. Photolysis was carried out in cyclohexane for 70–140 h using a mercury vapor lamp (450W) without excluding oxygen.

Irradation of Parsol 1789 in cyclohexane yielded tert-butylbenzene, p-tert-butylbenzoic acid and p-methoxybenzoic acid; products obtained from the combination of the sunscreen with the solvent included the cyclohexyl esters of p-methoxybenzoic acid, p-tert-butylbenzoic acid and methanoic acid; products obtained from the solvent included cyclohexanol, cyclohexanone and dicyclohexyl ether.

Irradiation of Oxybenzone in the cyclohexane for 100 h produced no detectable products by either gas or liquid chromatographic analysis. Oxybenzone was recovered unchanged and no products were observed from the photoinitiated reaction of oxygen with the solvent.

Irradiation of Padimate O in cyclohexane yielded the ethylhexyl esters of p-aminobenzoic acid, p-monomethylaminobenzoic acid and p-dimethylamino (o/m)-methylbenzoic acid, as well as products from the photoinitiated reaction of oxygen with the solvent.