Elastic behavior of non-Gaussian polymethylene chains

In this paper, elastic behaviors of non-Gaussian polymethylene (PM) chains with chain length N=100 are investigated by rotational isomeric state model. Here the tetrahedral lattice of PM chain and the non-local interaction of Sutherland potential are adopted. In the metropolis movement of PM chain, a four-bond movement model is used. The average energy and average Helmholtz free energy with various elongation ratios λ are calculated by Monte Carlo simulation method. The average energy increases with elongation ratio λ and the average Helmholtz free energy decreases with elongation ratio λ. The elastic force f and the energy contribution to elastic force f_u can be obtained from f=∂〈A〉/∂r and f=∂〈U〉/∂r. We find that the elastic force f increases with elongation ratio λ and the energy contribution f_u decreases with elongation ratio λ, and f_u is less than zero. The ratio f_u/f is close to −0.21 for λ?1.25, and −0.04 to −0.35 for λ>1.25 at T=364 K. In our calculation, the rubber elasticity may be discussed in terms of the chemical structure of polymer chains.     

Chirality changes in reactions of asymmetric molybdenum complexes

Optical rotatory dispersion and circular dichroism studies have allowed the determination of the changes in configuration at the molybdenum center upon displacement of carbonyl and iodide in neomenthylcyclopentadienyl—Mo(allyl)(NO)X systems. Displacement of carbonyl by iodide occurs with retention of configuration. Replacement of iodide with benzenesulfonate followed by replacement of the sulfonate with iodide occurs stereospecifically with net retention of configuration. In the case of cyclopentadienylMo(cyclooctenyl)(NO)I, the enantiomers were separated via a spontaneous resolution through crystallization of the complex in the space group P2₁2₁2₁. These studies have allowed the correlation not only of the absolute configuration at the metal center with CD studies, but also have established that a long wavelength optically active transition at approximately 400 nm can be correlated with endo-exo isomerism. Comparison of the rates of interconversion suggest that endo to exo isomerization occurs via a clockwise rotation of the allyl in the (R)-isomer. Crystallographic details: (—)-(S)-(NMCp)Mo(allyl)(NO)I crystallizes in the space group P2₁2₁2₁ with a 7.221(1), b 12.686(7), c 21.603(7) Å, Z = 4, V = 1979(2) ų; R₁ = 0.039, R₂ = 0.046; (—)-(S)-(Cp)Mo(cyclooctenyl)(NO)I crystallizes in the space group P2₁2₁2₁ with a 8.466(1), b 10.449(2), c 16.372(2) Å, Z = 4, V = 1448.3(6), R₁ = 0.038, and R₂ = 0.046.     

Crystal structure and magnetic structure of TbOOH

The monoclinic modification of terbium oxide hydroxide, TbOOH, was prepared using hydrothermal technique. The crystal structure was investigated by three-dimensional single-crystal X-ray analysis and was refined to a conventional R-value of 8.1%. The space group is $\text{P2}{}_1\text{m}$, No. 11, with a = 6.04 Å, b = 3.69 Å, c = 4.33 Å, and β = 109.0°. The terbium atom is seven coordinated with oxygen atoms, and the structure is not hydrogen bonded.The compound is antiferromagnetic with a Néel temperature of 10°K. Neutron diffraction powder patterns were measured at 300°K and 4.2°K. The magnetic super lattice reflections were indexed on the basis of a monoclinic unit cell with the dimensions a_M = 2a, b_M = b, c_M = c, and β_M = β, where a, b, c, and β are the dimensions of the chemical unit cell. The structure contains two independent magnetic atoms. A nonclinear antiferromagnetic arrangement of the spins describes the magnetic structure. The spin at one atom has an angle of 43° with the ac plane and the projection of the spin on the ac plane has an angle of 59° with the a axis. The spin on the other atom has an angle of ?43° with the ac plane, the projection having the same angle of 59° with the a axis.     

Photochemistry of dienones—X: Photochemistry of (e)-β-ionone oxime ethyl ether

(E)-β-ionone oximc ethyl ether [(E, E)-4] upon direct irradiation with λ either254or 313 nm yields the geometrical isomer (E, Z)-4 and (Z)-retro-γ-ionone oxime ethyl ether (Z,E)-5 as the sole primary products, illustrating (E)-(Z) isomerization (φ₃₁₃ =0.49) and a 1, 5-hydrogen shift (φ313 =0.15) respectively. From studies with triplet photosensitizers and with ethyl iodide (to enhance the singlet-triplet intersystem crossing) it is concluded that these two products in the direct irradiation result only from the singlet excited state, and that the inter-system crossing quantum yield is relatively low. Upon prolonged irradiation of (E,E)-4 with λ 313 nm the eventual products are (Z,E)-5 and (Z,Z)-5, whereas with λ 254 nm they are (E,E)-5 and [(Z,E)-5 and/or (E,Z)-5]. Upon triplet photosensitization (E,E)-4 undergoes only (E)-(Z) isomerization, leading to a mixture of all the four geometrical isomers of4. From the dependence of the geometrical isomer distribution in the photostationary state on the triplet energy of the sensitizer the triplet energies of (E,E)-4, (E, Z)-4, (Z, E)-4, and (Z, Z)-4 have been determined to be ca 55, < 55,57, and 57 $\text{kcal}\text{mol}$ respectively.     

Adiabatic compressibility of critical binary mixtures of nitroethane/isooctane and nitroethane/3-methylpentane

The adiabatic compressibility β_S of nitroethane/isooctane is measured from 18 to 900 Hz at reduced temperatures ? ranging from 5 × 10^-5 to 5 × 10^-2. The zero-frequency compressibility extrapolated from the data is related with the specific heat at constant pressure c_p through the theory of Ferrell and Bhattacharjee (FB). The coupling constant g is evaluated from this relation as 0.38, which agrees with that from the thermodynamic definition of g. β_S at 900 Hz is observed for nitroethane/3-methylpentane at ? 5 × 10^-5-6 × 10^-2. A linear plot of the critical part of β_S against 1n? gives g = 0.34, which agrees with g from the thermodynamic definition and also with that from ultrasonic absorption. Numerical values of the critical and background components of β_S, the isothermal compressibility β_T, c_p, the specific heat at constant volume c_v, and the thermal expansion coefficient α_p are calculated for the two mixtures. The expression of β_S from Anisimov's theory is found to be consistent with that from the FB theory.     

Linear expansion of the eigenvalues of a Hermitian matrix and its application to the analysis of the electronic spectra of 3d ions in crystals

It is shown that the eigenvalues E_i of a Hermitian matrix H with matrix elements H_ij = Σ_kA^k_ija_k, where A^k_ij are known numbers and a_k a set of parameters, can be exactly expanded as $\text{E}{}_{\mathrm{i}}\text{= Σ}{}_{\mathrm{k}}\text{(}\text{?E}{}_{\mathrm{i}}\text{?a}{}_{\mathrm{k}}\text{)a}{}_{\mathrm{k}}$. This property is applied to the analysis of the optical spectra of transition metal ions in crystals proposed by L. Pueyo, M. Bermejo, and J. W. Richardson (J. Solid State Chem.31, 217, 1980), and it is shown that this method represents the best fit of the Hamiltonian eigenvalues to the observed (or calculated) spectrum. Further advantages of using this property, in connection with the spectral analysis, are the minimization of the errors associated with the numerical approximations and a reduction in computer time. In the molecular orbital calculation of the optical or uv spectra of these systems, this linear expansion of the eigenvalues give a detailed interpretation of the improvements produced by refined calculations, such as those including configuration interaction. In particular, the changes in one-electron energy and in open-shell repulsion interactions associated with the refinement can be clearly and easily formulated. As examples, the computed spectra of CrF^4?₆ and CrF^3?₆ are discussed.     

Influences of Co-60 gamma-ray irradiation on electrical characteristics of Al2O3 MOS capacitors

Effects of gamma-ray irradiation on the electrical characteristics of Al₂O₃ MOS capacitors such as barrier height, acceptor concentration, series resistance and interface state parameters have been studied by analyzing capacitance–voltage (C–V) and conductance–voltage (G/ω–V) measurements. The fabricated MOS capacitors were irradiated with gamma-rays at doses up to five grays. C–V and G/ω–V measurements were recorded prior to and after irradiation at high frequency. The results show that the measured capacitance and conductance values decreased with increasing in irradiation dose and C–V and G/ω curves has been shifted toward the negative voltages. Moreover, the series resistance (R _s) and density of interface states increased with increasing in irradiation dose and density of interface states (D _it) were calculated as order of 10¹² eV^?1cm^?2 prior to and after irradiation. Due to presence and variations in the R _s values, the corrected and the measured C–V and G/ω–V exhibited different behaviors. Therefore other electrical characteristics were assessed from corrected C _c characteristics. It was observed that acceptor concentration decreased with increasing in barrier height of device due to changes in interface states and diffusion potential.     

Gradient expansion of the atomic kinetic energy functional

It is demonstrated that the ground-state atomic kinetic energy functional T[?], where ? is the electron density, can be computed to surprising accuracy from the truncated gradient expansion: T[?] = + T₂[?] + T₄[?], with T_o[?] = $\text{3}\text{10}$(3π²)$\text{2}\text{3}$ ∫ ?$\text{5}\text{3}$ d_τ, T₂ [?] = $\text{1}\text{72}$ ∫ (??)²?^?1 d_τ, and T₄ [?] given by the formula of Hodges. Calculations of T₀, T₂ and T₄ are reported for He with ? both the Hartree—Fock and a very accurate density, and for Ne, Ar and Kr with ? the Hartree—Fock density. For Kr, T₀ + T₂ + T₄ is within 0.3% of the exact Hartree—Fock T, with T₂/T₀ = 0.05, T₄/T₂ = 0.17.     

Lifetime measurements and stark mixing of autoionizing Cu I-states

Using a combination of collisional and laser excitation the lifetimes of 17 autoionizing Cu I states in the configurations 3d ⁹ 4s 6s and 3d ⁹ 4s4d were measured. The lifetimes are in the range of 1–50 ps and depend strongly on the coupling properties, the mixing with different configurations, and the radial integrals of the discrete with the continuum states. For the level 3d ⁹ 4s 4d ⁴ S _3/2 the influence of an electric field via Stark mixing of 3d ⁹ 4s 5p ⁴ P _1/2 on the autoionizing rate was investigated. The experimental values are compared with theoretical results which follow from ab initio calculations for the transition probabilities and least square fit values deduced from the experimental positions. Good agreement is found only for theJ=3/2 levels of both configurations 3d ⁹ 4s 4d and 3d ⁹ 4s 6s.     

Gas phase ion chemistry of molybdenum hexacarbonyl

In an ion cyclotron resonance (ICR) cell, Mo(CO)_n⁺ ions (n = 0–6), generated by electron ionization (EI) with 70 eV electrons, on collisions with Mo(CO)₆ undergo charge exchange (confirmed by isotopic experiments), collision-induced dissociation (CID), and association reactions to produce Mo_m(CO)_n⁺ ions (m = 1–6). Reactions are essentially complete within 9 s at a pressure of 3 × 10⁻⁹ Torr, as recorded by the manifold ion gauge (uncalibrated); Mo(CO)_n⁺ ions with n = 0–5 have been consumed within this time whereas Mo(CO)₆⁺ ions have achieved a steady concentration. All Mo₂(CO)_n⁺ ions (n = 0–11) were observed: the abundances of dimolybdenum-containing ions with n < 7 decrease at extended reaction times, whereas those with n ≥ 7 remain steady or increase slowly, implying that reactivity decreases with increasing CO content. The major dimers have n = 7, 9, and 10. When subjected to CID the Mo₂(CO)₇⁺ ion yields Mo₂(CO)_n⁺ ions (n = 0–6). Most Mo₃(CO)_n⁺ ions (n = 0–13) were observed, those with n = 9 being formed most readily. Similar observations apply to larger clusters, the most abundant ions being those with CO:Mo ratios of 2–3:1. Mo(CO)_n⁺ ions (n = 0, 3–6) formed by EI with 15 eV electrons are unreactive for reaction times of at least 5 s at the same pressure. General reaction sequences are proposed. Negative ions generated with 70 eV electrons (∼ 90% Mo(CO)₅⁻) are much less reactive but also lead to cluster ion formation on reaction with Mo(CO)₆.     

Chemoenzymatic synthesis of both enantiomers of 3-hydroxy- and 3-amino-3-phenylpropanoic acid

Ethyl (S)-3-hydroxy-3-phenylpropionate (S)-2 was obtained by the asymmetric reduction of ethyl 3-phenyl-3-oxopropionate 1 with the yeast Saccharomyces cerevisiae (ATCC 9080). The kinetic resolution of racemic ethyl 2-acetoxy-3-phenyl-propionate rac-3 with the same microorganism, gave after hydrolysis ethyl (R)- and (S)-3-hydroxy-3-phenylpropionates (R)-2 and (S)-2 which were converted by a straightforward series of reactions to the enantiomers of 3-amino-3-phenyl-propionic acids (S)-6 and (R)-6. The asymmetric reduction and hydrolytic kinetic resolution were also tested with several other whole cell systems under a variety of conditions.     

Efficient one-pot synthesis of 2-hydroxyethyl per-O-acetyl glycosides

A class of stereo-isomerically-pure alkanediol monoglycosides, 2-hydroxyethyl per-O-acetyl pyranosides (IIIa-IIIf), was conveniently prepared by a one-pot reaction of per-O-acetylated pyranoses (Ia-If) and 2-(tert-butyldimethylsilyloxy)ethanol (II) with catalysis by BF₃·OEt₂. The α-(IIIa) or β-linked glycosides (IIIb-IIIf) with 1,2-trans-configuration were obtained from glycosyl donors with participation of the neighbouring 2-O-acetyl group. BF₃·OEt₂, along with hydrogen fluoride released from BF₃·OEt₂ under the experimental conditions used, facilitates the subsequent de-protection of siloxane to successfully afford 2-hydroxyethyl per-O-acetyl-pyranosides.     

Fine structure and transition probabilities of the 2p 5 nl bound excited states of Ne atom

We present a semi-empirical calculational procedure for thep ⁵ nl bound excited states of rare gas atoms based on the use of an LS-dependent orbital for an excitednl electron outside a frozen Hartree-Fockp ⁵ core. The spin-orbit interaction is accounted for approximately using a localized Hartree potential. The contribution from the long-range core polarization is estimated by using a parametrized potential. A model potential is also introduced to represent partially the short-range multi-electron interactions for thep ⁵ np levels. The energy levels are calculated by diagonalizing the Hamiltonian matrix following anLS →jl transformation. The calculated fine structure of the Nep ⁵ ns,p ⁵ np,p ⁵ nd, andp ⁵ nf ¦ (jl)KJ〉 levels are in close agreement with the observed level splittings. The transition probabilities are also in agreement with earlier theoretical and experimental results.     

Structures of ordered tungsten- or molybdenum-containing quaternary perovskite oxides

The room temperature crystal structures of six A₂MMoO₆ and A₂MWO₆ ordered double perovskites were determined from X-ray and neutron powder diffraction data. Ba₂MgWO₆ and Ba₂CaMoO₆ both adopt cubic symmetry (space group Fm3?m, tilt system a⁰a⁰a⁰). Ba₂CaWO₆ has nearly the same tolerance factor (t=0.972) as Ba₂CaMoO₆ (t=0.974), yet it surprisingly crystallizes with I4/m symmetry indicative of out-of-phase rotations of the MO₆ octahedra about the c-axis (a⁰a⁰c^?). Sr₂ZnMoO₆ (t=0.979) also adopts I4/m symmetry; whereas, Sr₂ZnWO₆ (t=0.976) crystallizes with monoclinic symmetry (P2₁/n) with out-of-phase octahedral tilting distortions about the a- and b-axes, and in-phase tilting about the c-axis (a^?a^?c⁺). Ca₂CaWO₆ (t=0.867) also has P2₁/n symmetry with large tilting distortions about all three crystallographic axes and distorted CaO₆ octahedra. Analysis of 93 double perovskites and their crystal structures showed that while the type and magnitude of the octahedral tilting distortions are controlled primarily by the tolerance factor, the identity of the A-cation acts as the secondary structure directing factor. When A=Ba²⁺ the boundary between cubic and tetragonal symmetries falls near t=0.97, whereas when A=Sr²⁺ this boundary falls somewhere between t=1.018 and t=0.992.     

Measurement of dynamic properties of polymeric glasses for different modes of deformation

Methods for measuring various storage moduli and damping factors of glassy polymers in the frequency range 10^?2 to 10^?7 Hz are critically reviewed. At frequencies between about 10^?2 and 200 Hz, components of the complex tensile modulus E¹ and complex Poisson's ratio ν¹ have been determined at 21 °C for polymethyl methacrylate (PMMA) and rigid polyvinyl chloride (PVC) using a non-resonance technique with bidirectional strain gauges. From these measurments, components of the complex shear modulus G¹ and bulk modulus K¹ have been evaluated and shown to vary with frequency in a manner consistent with data obtained by other methods. Molecular motions responsible for the broad secondary relaxation regions in PMMA and PVC are thus able to couple with both shear and dilatational stress fields.     

Copolymerization of methyl 2-acetamidoacrylate and styrene in the presence of stannic chloride

Continuous variation method in UV revealed that methyl N-acetylaminoacrylate (MNA) and SnCl₄ formed the 1:1 complex. The copolymerization of MNA with styrene in tetrahydrofuran was carried out at 50 °C in the presence of SnCl₄. The resulting monomer reactivity ratios decreased with an increasing concentration of SnCl₄ added. This finding suggests that SnCl₄ participates in the propagation step of the copolymerization. Therefore, the copolymerization was analyzed by assuming terpolymerization of free MNA (M₁), complexed MNA (M₂), and styrene (M₃). The absolute copolymerization parameters were obtained as follows: k₁₁/k₁₂=0.165, k₁₁/k₁₃=3.04, k₂₂/k₂₁=0.32, k₂₂/k₂₃=0.103, k₃₃/k₃₁=0.058, k₃₃/k₃₂=0.001, Q₁=6.03, e₁=0.52, Q₂=88.57, and e₂=2.23. The complexed MNA is more reactive to polymer radicals with free MNA and styrene as the terminal unit than the free MNA. Very small values of k₂₂/k₂₃ and k₃₃/k₃₂ suggests that the copolymerization of the complexed MNA and styrene proceeds alternatingly.     

Measurement of impact parameter dependent probabilities and total cross sections for targetK-shell ionization by He+ ions

We have measured the impact parameter dependent K-shell ionization probabilitiesP _K (b) of Ca, Cr and Cu from collisions with 4.04 MeV He⁺ ions by particle-K X ray coincidences. A dependence on the target thickness was investigated to study a possible influence of multiple collisions onP _K (b). We measured the total cross section σ _K forK vacancy production simultaneously withP _K (b) and σ _K agrees within 30% with the integratedP _K (b). A comparison of theP _K (b) and σ _K with SCA calculations of Trautmann et al. using RHFS wavefunctions for united atom and separated atom states is discussed.     

Experimental and theoretical study of the hyperfine structure in the (5d+6s)96p configurations of Pt I

The hyperfine structure of the odd configurations 5d ⁹6p and 5d ⁸6s6p was studied with laser optogalvanic spectroscopy and high resolution interferometry in a platinum hollow cathode. A parametric hyperfine structure analysis for the configurations (5d+6s)⁹6p with 10 excited odd-parity levels was performed for¹⁹⁵Pt. We obtained one-electron hfs parameters,a _5d ⁰¹ =1160(320) MHz,a _6s ¹⁰ =35600(5300) MHz anda _6p ⁰¹ =1300(780) MHz for the configuration 5d ⁸6s6p. The corresponding $\left\langle {r^{ - 3} } \right\rangle _{nl}^{k_s k_l } $ values are compared with those known for other 5d-elements.     

Identification of new lines in the beam-foil spectrum of B II–IV

Ten, six, and twenty-one new lines appearing in the beam-foil spectra of boron (30–200 nm) have been identified in B II, B III, and B IV, respectively. Energies have been determined with higher accuracy than obtained before for the 2p3s ¹ P ⁰, 2s6d ³ D, 2p3p ³ D, 2p3p ³ S, 2p3p ³ P, and 2p3p ¹ D terms in B II. First energy values are also reported for the 2s6d ¹ D and 2s7d ³ D terms in B II.