Correlation between Hammett substituent constants and directly calculated pi-conjugation strength

The results of an energy decomposition analysis of ortho-, meta-, and para-substituted benzylic cations and para-substituted benzylic anions H2C-C6H4Rq (R = H, F, CN, Me, OH, NH2, NO2, CHO, CO2H; q = +, -) are presented and discussed. The calculated values for the pi bonding between CH2(q) and C6H4R show for substituents which have pi orbitals a linear correlation with the Hammett sigma(p), sigma(+)(p), and sigma(m) constants.     

Unitary matrices for phase-coded holographic memories

We propose a novel type of unitary matrix for phase-code multiplexed holographic memories, which could be quickly generated from geometric sequences. Our analysis shows that the phase-code matrices are unitary rather than orthogonal. The new matrices have complex elements. The order of unitary matrices can be any positive integer, so that we can accommodate the available spatial light modulators to obtain the maximum possible storage capacity. The cross-talk noises in phase-encoded memories with unitary matrices and with Hadamard matrices are of the same order of magnitude, which are much lower than those in holographic memories with wavelength multiplexing or angle multiplexing.     

Development of Methods to Determine the Infrared-Optical Properties of Polymer Films

Summary: In this paper, two methods for the determination of infrared optical properties of thick polymer films, based on FTIR spectroscopy, were implemented and used. Complex index of refraction data were generated for various ethylene copolymer films. Transmittance and reflectance spectra were measured in the mid infrared range using a gold-coated 100 mm-diameter integrating sphere. For the investigated films n and k values ranging from 1.3 to 1.6 and from 10⁻⁴ to 0.25 were determined, respectively. Regarding n, a good agreement was obtained for both methods, the transmittance/reflectance procedure (T/R method) used for transparent and semitransparent regions, and Single Substractive Kramers-Kronig (SSKK) algorithm applied for non-transparent regions. The highest k values were determined for the CH₂ stretching vibration. The k values are dependent on comonomer content and film thickness. The combination of both methods allows for an accurate determination of n and k in the entire IR region relevant for solar application.     

Spectroscopical Investigation of Ski Base Materials

Summary: Raman spectroscopy was applied to perform a comprehensive morphological analysis of polyethylene (PE) ski base materials at different processing levels. The morphological characterization included determination and evaluation of Raman spectra and examination of the crystallinity values by differential scanning calorimetry (DSC). A good agreement between Raman and DSC crystallinity fractions was obtained, thus corroborating the Raman spectroscopy approach. While for the PE grade with the lowest average molar mass no significant morphological changes due to processing from the raw material via the extruded film to the post-treated film was found, higher molar mass PE grades exhibited a decrease of crystallinity, but an increase of the amorphous fraction along the process chain.     

The facile reduction of carbon dioxide to carbon monoxide with an amido-digermyne

Taking the fizz out: A digermyne compound with a Ge?Ge single bond has been shown to quantitatively reduce CO(2) to CO at temperatures as low as -40?°C. The mechanism of this unprecedented reaction has been probed by spectroscopic and computational techniques and involves a metastable intermediate (see picture; Ar*=C(6) H(2) {C(H)Ph(2) }(2) Me-2,6,4).     

Direct measurements of the high temperature rate constants of the reactions NCN + O, NCN + NCN, and NCN + M

The rate constant of the reaction NCN + O has been directly measured for the first time. According to the revised Fenimore mechanism, which is initiated by the NCN forming reaction CH + N(2)→ NCN + H, this reaction plays a key role for prompt NO(x) formation in flames. NCN radicals and O atoms have been quantitatively generated by the pyrolysis of NCN(3) and N(2)O, respectively. NCN concentration-time profiles have been monitored behind shock waves using narrow-bandwidth laser absorption at a wavelength of λ = 329.1302 nm. Whereas no pressure dependence was discernible at pressures between 709 mbar < p < 1861 mbar, a barely significant temperature dependence corresponding to an activation energy of 5.8 ± 6.0 kJ mol(-1) was found. Overall, at temperatures of 1826 K < T < 2783 K, the rate constant can be expressed as k(NCN + O) = 9.6 × 10(13)× exp(-5.8 kJ mol(-1)/RT) cm(3) mol(-1) s(-1) (±40%). As a requirement for accurate high temperature rate constant measurements, a consistent NCN background mechanism has been derived from pyrolysis experiments of pure NCN(3)/Ar gas mixtures, beforehand. Presumably, the bimolecular secondary reaction NCN + NCN yields CN radicals hence triggering a chain reaction cycle that efficiently removes NCN. A temperature independent value of k(NCN + NCN) = (3.7 ± 1.5) × 10(12) cm(3) mol(-1) s(-1) has been determined from measurements at pressures ranging from 143 mbar to 1884 mbar and temperatures ranging from 966 K to 1900 K. At higher temperatures, the unimolecular decomposition of NCN, NCN + M → C + N(2) + M, prevails. Measurements at temperatures of 2012 K < T < 3248 K and at total pressures of 703 mbar < p < 2204 mbar reveal a unimolecular decomposition close to its low pressure limit. The corresponding rate constants can be expressed as k(NCN + M) = 8.9 × 10(14)× exp(-260 kJ mol(-1)/RT) cm(3) mol(-1) s(-1)(±20%).     

The nature of Ru-NO bonds in ruthenium tetraazamacrocycle nitrosyl complexes--a computational study

Ruthenium complexes including nitrosyl or nitrite complexes are particularly interesting because they can not only scavenge but also release nitric oxide in a controlled manner, regulating the NO-level in vivo. The judicious choice of ligands attached to the [RuNO] core has been shown to be a suitable strategy to modulate NO reactivity in these complexes. In order to understand the influence of different equatorial ligands on the electronic structure of the Ru-NO chemical bonding, and thus on the reactivity of the coordinated NO, we propose an investigation of the nature of the Ru-NO chemical bond by means of energy decomposition analysis (EDA), considering tetraamine and tetraazamacrocycles as equatorial ligands, prior to and after the reduction of the {RuNO}(6) moiety by one electron. This investigation provides a deep insight into the Ru-NO bonding situation, which is fundamental in designing new ruthenium nitrosyl complexes with potential biological applications.     

Stationary two-black-hole configurations: A non-existence proof

Based on the solution of a boundary problem for disconnected (Killing) horizons and the resulting violation of characteristic black hole properties, we present a non-existence proof for equilibrium configurations consisting of two aligned rotating black holes. Our discussion is principally aimed at developing the ideas of the proof and summarizing the results of two preceding papers (Neugebauer and Hennig, 2009 [2], Hennig and Neugebauer, 2011 [3]). From a mathematical point of view, this paper is a further example (Meinel et al., (2008) [29]) for the application of the inverse (“scattering”) method to a non-linear elliptic differential equation.     

Transition‐Metal Complexes of Tetrylones [(CO)5W‐E(PPh3)2] and Tetrylenes [(CO)5W‐NHE] (E=C–Pb): A Theoretical Study

Quantum chemical calculations at the BP86/TZVPP//BP86/SVP level are performed for the tetrylone complexes [W(CO)₅‐E(PPh₃)₂] ( W‐1 E ) and the tetrylene complexes [W(CO)₅‐NHE] ( W‐2 E ) with E=C–Pb. The bonding is analyzed using charge and energy decomposition methods. The carbone ligand C(PPh₃) is bonded head‐on to the metal in W‐1 C , but the tetrylone ligands E(PPh₃)₂ are bonded side‐on in the heavier homologues W‐1 Si to W‐1 Pb . The W? E bond dissociation energies (BDEs) increase from the lighter to the heavier homologues ( W‐1 C : D_e=25.1 kcal mol^?1; W‐1 Pb : D_e=44.6 kcal mol^?1). The W(CO)₅←C(PPh₃)₂ donation in W‐1 C comes from the σ lone‐pair orbital of C(PPh₃)₂, whereas the W(CO)₅←E(PPh₃)₂ donation in the side‐on bonded complexes with E=Si–Pb arises from the π lone‐pair orbital of E(PPh₃)₂ (the HOMO of the free ligand). The π‐HOMO energy level rises continuously for the heavier homologues, and the hybridization has greater p character, making the heavier tetrylones stronger donors than the lighter systems, because tetrylones have two lone‐pair orbitals available for donation. Energy decomposition analysis (EDA) in conjunction with natural orbital for chemical valence (NOCV) suggests that the W? E BDE trend in W‐1 E comes from the increase in W(CO)₅←E(PPh₃)₂ donation and from stronger electrostatic attraction, and that the E(PPh₃)₂ ligands are strong σ‐donors and weak π‐donors. The NHE ligands in the W‐2 E complexes are bonded end‐on for E=C, Si, and Ge, but side‐on for E=Sn and Pb. The W? E BDE trend is opposite to that of the W‐1 E complexes. The NHE ligands are strong σ‐donors and weak π‐acceptors. The observed trend arises because the hybridization of the donor orbital at atom E in W‐2 E has much greater s character than that in W‐1 E , and even increases for heavier atoms, because the tetrylenes have only one lone‐pair orbital available for donation. In addition, the W? E bonds of the heavier systems W‐2 E are strongly polarized toward atom E, so the electrostatic attraction with the tungsten atom is weak. The BDEs calculated for the W? E bonds in W‐1 E , W‐2 E and the less bulky tetrylone complexes [W(CO)₅‐E(PH₃)₂] ( W‐3 E ) show that the effect of bulky ligands may obscure the intrinsic W? E bond strength.     

Design of neutral Lewis superacids of group 13 elements

A general approach toward superstrong neutral Lewis acids, featuring both the pyramidalization of acceptor molecules and the introduction of electron-withdrawing substituents, is proposed and examined theoretically. Complexes of group 13 element derivatives with ammonia at the B3LYP and MP2 levels of theory with def2-TZVPP basis set are considered as examples. Pyramidalization of the acceptor molecule significantly increases its Lewis acidity (by 50-60 kJ mol(-1) for aluminum and gallium compounds and by 120-130 kJ mol(-1) for boron compounds). An additional increase of the complex stability of 55-75 kJ mol(-1) may be achieved by fluorination. The combined increase of the bond dissociation energy amounts to 110-190 kJ mol(-1), which is equivalent to 19-33 orders of magnitude in Lewis acidity.