Model based prediction of the trap limited diffusion of hydrogen in post‐hydrogenated amorphous silicon

The diffusion of hydrogen within an hydrogenated amorphous silicon (a‐Si:H) layer is based on a trap limited process. Therefore, the diffusion becomes a self‐limiting process with a decreasing diffusion velocity for increasing hydrogen content. In consequence, there is a strong demand for accurate experimental determination of the hydrogen distribution. Nuclear resonant reaction analysis (NRRA) offers the possibility of a non‐destructive measurement of the hydrogen distribution in condensed matter like a‐Si:H thin films. However, the availability of a particle accelerator for NRR‐analysis is limited and the related costs are high. In comparison, Fourier transform infrared spectroscopy (FTIR) is also a common method to determine the total hydrogen content of an a‐Si:H layer. FTIR spectrometers are practical table‐top units but lack spatial resolution. In this study, an approach is discussed that greatly reduces the need for complex and expensive NRR‐analysis. A model based prediction of hydrogen depth profiles based on a single NRRA measurement and further FTIR measurements enables to investigate the trap limited hydrogen diffusion within a‐Si:H. The model is validated by hydrogen diffusion experiments during the post‐hydrogenation of hydrogen‐free sputtered a‐Si. The model based prediction of hydrogen depth profiles in a‐Si:H allows more precise design of experiments, prevents misinterpretations, avoids unnecessary NRRA measurements and thus saves time and expense. (© 2016 WILEY‐VCH Verlag GmbH &Co. KGaA, Weinheim)     

Direct computation of second-order SCF properties of large molecules on workstation computers with an application to large carbon clusters

Summary The ab initio SCF computation of second-order properties of large molecules (with 50 atoms or more) on workstation computers is demonstrated for static dipole polarizabilities and nuclear magneting shieldings. The magnetic shieldings are calculated on the basis of gauge including atomic orbitals (GIAO). Algorithmic advances (semi-direct algorithms with efficient integral pre-screening, and use of a quadratically convergent functional for the polarizabilities) are presented together with an illustrative application to the fullerenes C₆₀ and C₇₀.     

Zur Bildung und Struktur der Phosphinophosphiniden-phosphorane tBu2P?PP(Me)tBu2 1, tBu(Me3Si)P?PP(Me)tBu2 2 und tBu2P?PP(Br)tBu2 3

Synthesis and Structure of Phosphinophosphinidene-phosphoranes tBu₂P? P?P(Me)tBu₂ 1, tBu(Me₃Si)P? P?P(Me)tBu₂ 2, and tBu₂P? P?P(Br)tBu₂ 3 A new method for the synthesis of 1 and 2 (Formulae see ?Inhaltsübersicht”?) is reported based on the reaction of 5 with substitution reagents (Me₂SO₄ or CH₃Cl). The results of the X-ray structure determination of 1 and 2 are given and compared with those of 3 . While in 3 one P? P distance corresponds to a double bond and the other P? P distance to a single bond (difference 12.5 pm) the differences of the P? P distances in 1 and 2 are much smaller: 5.28 pm in 1 , 4.68 pm in 2 . Both 1 and 2 crystallize monoclinic in the space group P2₁/n (Z = 4). 2 additionally contains two disordered molecules of the solvent pentane in the unit cell. Parameters of 1 : a = 884.32(8) pm, b = 1 924.67(25) pm, c = 1 277.07(13) pm, β = 100.816(8)°, and of 2 : a = 1 101.93(12) pm, b = 1 712.46(18) pm, c = 1 395.81(12) pm, β = 111.159(7)°, all data collected at 143 K. The skeleton of the three P atoms is bent (PPP angle 100.95° for 1 , 100.29° for 2 and 105.77° for 3 ). Ab initio SCF calculations are used to discuss the bonding situation in the molecular skeleton of the three P atoms of 1 and 3 . The results show a significant contribution of the ionic structure R₂P? P(^?)? P(⁺)(X)R₂. The structure with (partially) charged P atoms is stabilized by bulky polarizable groups R (as tBu) as compared to the fully covalent structure R₂P? P(X)? PR₂.     

Anab initio investigation of Cu2Se and Cu4Se2

Summary Experimentally known copper selenium clusters show extraordinary geometrical features, especially short Cu-Cu distances. We report the first theoretical investigation of Cu₂Se and Cu₄Se₂. Various quantum chemical methods (SCF, MP2, CPF, CCSD, CCSD(T), LDF) are applied to determine the importance of dynamic electron correlation. We find that inclusion of correlation does not essentially change the electronic structure of the clusters but has a strong influence on geometries. To reduce the computational effort we apply effective core potentials (ECPs) in combination with small, but carefully optimized basis sets. The applicability of simple modellings of correlation energies for approximate inclusion of correlation effects in SCF geometry optimizations is tested.     

The Radical Anions of N,N′-Dicyanoquinone Diimines,a New Class of Electron Acceptors

The radical anions of 12 N,N′-dicyanoquinone diimines, a new class of electron acceptors, hace been characterized by their hyperfine data with the use of ESR and ENDOR spectroscopy. The largest coupling constant (0.30–0.45 mT), due to the two ¹⁴N nuclei in the exocyclic positions, gives rise to a conspicuous broadening of the peripheral ESR lines by an incomplete averaging of the hyperfine anisotropy. The most plausible interpretation of the experimental results for the radical anions of N,N′-dicyano- 1,4-benzoquinone diimine ( 1 ) and N,N′-Dicyano-9,10-anthraquinone diimine ( 9 ) is in terms of both ‘syn’- and ‘anti’-configurations contributing to the ESR and ENDOR spectra and having equal proton- and ¹⁴N-coupling constants. The π-spin distribution in the radical anions of N,N′-dicyanoquinone diimines is compared with those in the analogous ions of tetracyanoquinodimethanes and quinones.     

Matrix-Untersuchungen zu monomerem Kupfer(I)-chlorid und seinen Komplexen mit N2 und PN IR-spektroskopische Nachweise und ab-initio Rechnungen

Matrix-Investigations on Monomeric Copper(I) Chloride and its Complexes with N₂ and PN Ligands. IR Spectroscopic Results and ab-initio Calculation In solid argon the reaction of monomeric CuCl with N₂ yields ClCuN₂. On the basis of two absorptions in the ir-spectrum and their corresponding isotopic shifts (_14/15N) and with the help of a normal coordinate analysis, linearity of the molecule has been deduced. These results are confirmed by large scale ab-initio Calculations (CPF, MP2). Reaction of monomeric CuCl with molecular PN under matrix condition is shown to give rise to new absorptions in the IR spectrum which arev assigned to a linear molecule ClCuNP.     

Synthesis and characterization of functionalized water soluble cationic poly(ester amide)s

A new family of positively charged, water soluble and functional amino acid‐based poly(ester amide)s ( Arg‐AG PEA ) consisting of four building blocks (L ‐Arginine, DL ‐2‐Allylglycine, oligoethylene glycol, and aliphatic diacid) were synthesized by the solution copolycondensation. Functional pendant carbon–carbon double bonds located in the DL ‐2‐allylglycine unit were incorporated into these Arg‐AG PEAs, and the double bond contents could be adjusted by tuning the feed ratio of L ‐arginine to DL ‐2‐allylglycine monomers. Chemical structures of this new functional Arg‐AG PEA family were confirmed by Fourier transform infrared spectroscopy (FTIR) and nuclear magnetic resonance (NMR) spectra. The thermal property of these polymers was investigated; increasing the methylene chain in both the amino acid and diacid segments resulted in a reduction in the polymer glass‐transition temperature. All these cationic Arg‐AG PEAs had good solubility in water and polar organic solvents. The cytotoxity of Arg‐AG PEAs was evaluated by 3‐(4,5‐Dimethylthiazol‐2‐yl)‐2,5‐diphenyltetrazolium bromide (MTT) assay. These preliminary MTT results indicated that Arg‐AG PEAs were nontoxic to bovine aortic endothelial cells (BAECs). © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 48: 3758–3766, 2010     

A Model for the Cobalamin-Dependent Methionine Synthase

The acid-catalyzed transfer of a Me group from N,N-dimethylaniline ( 6 ) to vitamin-B₁₂-derived Co^I complexes 2a , b was realized (Scheme 3). Hexane-1-thiol ( 8 ) was methylated by the methylcobalt complexes 4a , b in the presence of pyridine. Conditions for the complete cycle, i.e., Me transfer from 6 to 8 with Co^I complexes acting as a nucleophile and a nucleofuge have been established. The importance of Zn²⁺ as activating agent and of the basicity of tertiary amines for the Me transfer has been investigated.