Update: Empirical determinations of the effective absorption coefficients for the NO γ-bands at 2259A and the ν3-fundamental of N2O at 4.52 μ [JQSRT 21, 475 (1979)]

Used of the revised Voigt parameter aT/p = (2150±200)°K/atm for argon-broadened NO γ-bands introduces no corrections into our previously published kinetics data but leads to a high revised effective value f₀₀=g₀₀f=7.34×10^-4 (+29%, - 16%) for the (0, 0)-band.     

Electron scattering from 70Ge and 72Ge

Cross sections have been measured for the elastic and inelastic scattering of electrons from ⁷⁰Ge and ⁷²Ge for momentum transfers from 0.65 to 1.14 fm^?1. Values for the parameters of a Fermi type ground-state charge distribution were obtained from a phase shift analysis of the elastic cross sections. The rms charge radius corresponding to these parameters is 4.07±0.02 fm for ⁷⁰Ge and 4.05±0.03 fm for ⁷²Ge. Using DWBA analysis the reduced transition probabilities for the electroexcitation of the 2₁⁺ and 3₁^? states were found to be: B(E2, ω)↑ = 19.7±1.2, 26.8±2.0 W.u.; B(E3, ω)↑ = 36±5, 37±7 W.u. for ⁷⁰Ge and ⁷²Ge respectively. The J^π = 3^? assignments for the state at 2.562 MeV in ⁷⁰Ge and 2.515 MeV in ⁷²Ge are confirmed.     

The adsorption of polymerized rodlike micelles at the solid-liquid interface

Solutions of rodlike polymeric micellar aggregates, formed from the polymerization of cetyltrimethyl-ammonium 4-vinylbenzoate (CTVB), adsorb at the solid-liquid interface. The poly-CTVB aggregates are imaged in situ using soft contact atomic force microscopy. The aggregates form self-organized two-dimensional films that show a high degree of order on nanometer to micrometer length scales. Unlike their simple surfactant analogues, the adsorbed layer structures are permanently adsorbed and the structure is resilient to washing with pure solvent. In the case of poly-CTVB, the adsorbed aggregates appear to be rigid cylindrical structures of between 30 and 60 nm in length. At the interface, the center to center spacing of the aligned aggregates is 8+/-1 nm. Images of a second series ofpolymerized aggregates formed by the copolymerization of CTVB with sodium vinyltosylate revealed a change in the aggregate structure to a set of linked spherical aggregates. These polymerized aggregates also spontaneously form a permanent adsorbed layer at the solid-liquid interface.     

Complete relative stereochemistry of multiple stereocenters using only residual dipolar couplings

Residual dipolar couplings (RDCs), in combination with molecular order matrix calculations, were used to unambiguously determine the complete relative stereochemistry of an organic compound with five stereocenters. Three simple one-dimensional experiments were utilized for the measurements of (13)C-(1)H, (13)C-(19)F, (19)F-(1)H, and (1)H-(1)H RDCs. The order matrix calculation was performed on each chiral isomer independently. The fits were evaluated by the comparison of the root-mean-square deviation (rmsd) of calculated and measured RDCs. The order tensor simulations based on two different sets of RDC data collected with phage and bicelles are consistent. The resulting stereochemical assignments of the stereocenters obtained from using only RDCs are in perfect agreement with those obtained from the single-crystal X-ray structure. Six RDCs are found to be necessary to run the simulation, and seven are the minimum to get an acceptable result for the investigated compound. It was also shown that (13)C-(1)H and (1)H-(1)H RDCs, which are the easiest to measure, are also the most important and information-rich data for the order matrix calculation. The effect of each RDC on the calculation depends on the location of the corresponding vector in the structure. The direct RDC of a stereocenter is important to the configuration determination, but the configuration of stereocenters devoid of protons can also be obtained from analysis of nearby RDCs.     

An initial value problem in rectilinear flow of a thermo-viscoelastic material with memory

Zusammenfassung Die Grundgleichungen für eine Theorie der Thermo-Viskoelastizität von Stoffen mit Gedächtnis werden auf das Problem der gradlingen Schichtströmung zwischen zwei Wärmespeichern angewandt. Es werden die Geschwindigkeit, die Spannungen und die Wärmeströmung bestimmt.

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Acknowledgement. This work was sponsored by the National Science Foundation under Research Grant NSF GK99.     

Three-dimensional packing structure and electronic properties of biaxially oriented poly(2,5-bis(3-alkylthiophene-2-yl)thieno[3,2-b]thiophene) films

We use a systematic approach that combines experimental X-ray diffraction (XRD) and computational modeling based on molecular mechanics and two-dimensional XRD simulations to develop a detailed model of the molecular-scale packing structure of poly(2,5-bis (3-tetradecylthiophene-2-yl)thieno[3,2-b]thiophene) (PBTTT-C(14)) films. Both uniaxially and biaxially aligned films are used in this comparison and lead to an improved understanding of the molecular-scale orientation and crystal structure. We then examine how individual polymer components (i.e., conjugated backbone and alkyl side chains) contribute to the complete diffraction pattern, and how modest changes to a particular component orientation (e.g., backbone or side-chain tilt) influence the diffraction pattern. The effects on the polymer crystal structure of varying the alkyl side-chain length from C(12) to C(14) and C(16) are also studied. The accurate determination of the three-dimensional polymer structure allows us to examine the PBTTT electronic band structure and intermolecular electronic couplings (transfer integrals) as a function of alkyl side-chain length. This combination of theoretical and experimental techniques proves to be an important tool to help establish the relationship between the structural and electronic properties of polymer thin films.