Hydrodynamic screening of ring copolymer solutions

The relaxation frequency of the dynamic correlation function for a diblock cyclic copolymer in solution in the zero average condition is calculated in the presence of hydrodynamic interaction. The latter is introduced through the screened Oseen tensor where the hydrodynamic screening length is used as a parameter to determine the range of screening. Substantial differences with the case of linear homopolymer are found, especially in the low q range where the dynamics are much faster and correspond to nondiffusive processes as usually is the case for copolymer systems. As the screening length decreases the dynamics approach the Rouse behavior and the minimum of the relaxation frequency shifts to lower values. The proportionality constant of the relaxation frequency in the intermediate q range Γ(q) → q³/(k_BTη₀) is also investigated as a function of the screening length. © 1994 John Wiley & Sons, Inc.     

Tilt and temperature dependence of the pitch in the chiral smectic C phase

Abstract

The chirality of the constituent molecules in the chiral smectic phase induces a helical structure with a pitch, p ₀. Because of the tilt and chirality there is a spontaneous polarization and a bend deformation which act upon the induced helix. The resulting pitch is described as a function of p ₀ using the phenomenological theory of a chiral smectic C phase. The pitch, p ₀, is then calculated using a molecular theory of the cholesteric phase. The results obtained explain the experimental observations, at least qualitatively.     

On the excitonic nature of the first UV absorption peak in polyene

The first absorption peak in the UV spectrum of polyene is interpreted in terms of charge transfer excitons. The exciton spectrum has been calculated from first principles using the Green's function formalism of charge transfer exciton theory. Electron correlation effects on the polyene band structure have been included with the help of second order Møller-Plesset perturbation theory and of the electron polaron model of Toyozawa. The spectrum of bound singlet excitons starts at E_K=0 = 1.86 eV above the top of the valence band. A deeper lying triplet level is observed at 0.72 eV. Further correlation effects on the band gap and dielectric screening of the electron-hole ineraction are discussed.     

Discrete-spectrum contribution to the Lamb-shift of the 2S and 2P hydrogenic states

A general formula due to Moses [Phys. Rev. A8, 1710 (1973)] for exact electric and magnetic multipole transition matrix elements in nonrelativistic hydrogenic atoms is reduced by carrying out additional integrations. By using the obtained reduced formula unrenormalized (finite) and renormalized Lamb-shift contributions stemming from individual discrete states as well as from the whole discrete spectrum are calculated in the case of the states 2S and 2P.     

Studies on the internal structure of the binary mixtures of N,N-dimethylacetamide with 2-methoxyethanol, 2-ethoxyethanol, 2-propoxyethanol and 2-butoxyethanol by means of measuring their densities and relative permittivities at 298.15 K

ABSTRACT

The densities and relative permittivities of binary mixtures of N,N-dimethylacetamide with 2-methoxyethanol, 2-ethoxyethanol, 2-propoxyethanol and 2-butoxyethanol have been measured as a function of composition, at T = 298.15 K. From the experimental data the excess molar volume (V^E) from a mole fraction and the excess relative permittivity (ε^E) from a volume fraction average have been calculated. The results are discussed in terms of intermolecular interactions and structure of studied binary mixtures.     

The geometry of the nitroguanyl fragment in the simplest nitroguanidine derivatives in the absence of intermolecular interactions: The gas electron diffraction data on 1,1,3,3-tetramethyl-2-nitroguanidine

The structures and force fields of the equilibrium forms of 2-nitroguanidine (1), 1,1,3,3-tetramethyl-2-nitroguanidine (2), and nitroguanyl azide (3) were determined in the MP2(full)/6-311G(3df, 2p) approximation; wagging-inversion motions of the N amine atoms were studied. The internal rotation potential function of the NO₂ group was calculated for 1. Similar functions for 1 and 2 were also obtained in the MP2(full)/6-311G(d, p) approximation. Direct one-dimensional problems for a nonrigid model were solved by the variational method, and the distribution of torsional levels was obtained. In the region of potential minimum, rotation in both molecules had the character of large-amplitude motions. For the first time, electron diffractions data were obtained at 100°C for molecule 2 without noticeable traces of substance decomposition. A structural r _e analysis was performed using the model of large-amplitude motions for characteristic NO₂ group torsional vibrations. Vibrational corrections to internuclear distances and mean amplitudes were calculated taking into account nonlinear kinematic effects using the force fields obtained in this work. The geometry of molecule 2 calculated in the MP2(full)/6-311G(3df, 2p) approximation well corresponds to the gas electron diffraction data. The parameters of molecule 2 in the crystalline phase, however, differ substantially from the parameters of the free molecule. This corresponds with the suggestion of the influence of intermolecular H-bonds involving the imine nitrogen atom and nitro groups oxygen atoms.     

Calculations of D‐wave bound states and resonance states of the screened helium atom using correlated exponential wave functions

We have investigated the effects of screened Coulomb (Yukawa) potentials on the bound ^1,3D states and the doubly excited ^1,3 D^e resonance states of helium atom using highly correlated exponential basis functions. The Density of resonance states are calculated using stabilization method. Highly correlated exponential basis functions are used to consider the correlation effect between the charged particles. A total of 18 resonances (nine each for ¹ D^e and ³ D^e states) below the n = 2 He ⁺ threshold has been calculated. For each spin states, this includes four members in the 2pnp series, three members in the 2snd series, and two members in 2pnf series. The resonance energies and widths for various screening parameters ranging from infinity to a small value for these ^1,3 D^e resonance states are reported along with the bound‐excited 1s3d ^1,3 D state energies. Overall behavior of the spectral profile of 1s3d ¹D state of helium atom due to electron‐electron and electron‐nucleus screening are also presented. Accurate resonance energies and widths are also reported for He in vacuum. © 2009 Wiley Periodicals, Inc. Int J Quantum Chem, 2010     

On the quantum chemical origin for the nonvalidity of Koopmans' theorem in transitionmetal compounds

The quantum chemical origin for the nonvalidity of Koopmans' theorem in transitionmetal compounds of the 3d series is analyzed by means of the Green's function formalism applied in the framework of a semiempirical INDO Hamiltonian. In the case of ferrocene (1), cyclobutadiene iron tricarbonyl (2) and irontetracarbonyl dihydride (3) the self-energy part of a geometric approximation has been partitioned into relaxation and correlation (pair removal, pair relaxation) increments. The breakdown of Koopmans' theorem for strongly localized MOs with large Fe 3d amplitudes is predominantly the result of electronic relaxation lowering the calculated ionization potentials. On the other hand the variation of the pair correlation energy in the cationic hole-state is by no means negligible and acts into the opposite direction as the relaxation increment. These significant pair relaxation contributions explain the wellknown failtures of the ΔSCF approach in combination with large scaleab initio bases. The loss of ground state pair correlation in the outer valence region is small in comparison to relaxation and pair relaxation. The magnitude of the aforementioned reorganization increments has been studied as a function of the localization properties of the MOs and as a function of the one-electron energies of the available particle- and hole-states. The computational findings derived with the INDO model are compared with recentab initio studies.     

Effektive Kernladungszahlen von Atomen der L-Schale

Zusammenfassung Die Ionisierungsenergien aller Atome und Ionen der L-Schale im Grundzustand und in den wichtigsten Valenzzuständen werden mit Hilfe eines einfachen Abschirmmodells unter Verwendung von wasserstoffähnlichen Einelektronenfunktionen gleichzeitig mit den Orbitalexponenten der Funktionen berechnet. Bei den Atomen wurden auch die Gesamtenergien durch Summierung sukzessiver Ionisierungspotentiale bestimmt. Die Übereinstimmung aller berechneten Größen mit dem experimentellen Material und mit den entsprechendenHartree-Fock-Energien ist überraschend gut. Das verwendete einfache Modell wird mit der analytischenSCF-Theorie verglichen.

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Effective nuclear charges for the atoms of the L-shell (Simple one center functions in LCAO-MO-Calculations, II)

Ionization energies for all atoms and ions of the L-shell in the ground state and in the most important valence states were calculated together with the orbital exponents of the atomic functions using a simple screening model and hydrogenlike functions. In the case of the neutral atoms the total energies were calculated as well by summation of successive ionization potentials. All the calculated energies agree very well with the experimental data and theHartree-Fock energies. The simple model used is compared with the analyticalSCF-theory.

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Mitt.:P. Schuster, Chem. Physics Letters1, 73 (1967).     

A study for structure and inter-diffusion coefficient of liquid K1− x Cs x metal alloys

Inter-diffusion coefficients of liquid K_{1? x} Cs _x metal alloys are calculated using scaling law proposed by Samanta et al. [A. Samanta, Sk.M. Ali, and S.K. Ghosh, Phys. Rev. Lett. 87, 245901 (2001)] following Dzugutov [M. Dzugutov, Nature 381, 137 (1996)], which express the possible relationship between the excess entropy and diffusion coefficient. The interatomic interactions are described from the individual version of the electron–ion potential proposed by Fiolhais et al. [C. Fiolhais, J.P. Perdew, S.Q. Armster, J.M. McLaren, and M. Brajczewska, Phys. Rev. B 51, 14001 (1995)]. The partial pair distribution functions and structure factors are calculated from the solution of Ornstein–Zernike integral equation with Rogers–Young closure. The evaluations with the composition of static structure and the inter-diffusion properties are discussed.     

Structure of Liquid Metals

Abstract

The structure factors and radial distribution functions of liquid sodium and aluminium were calculated using the Hypernetted chain equation and the Machin-Woodhead-Chihara (MWC) integral equation. Various oscillatory potentials suggested for these metals were considered in an attempt to determine the applicability of these integral equations for these potentials. The calculated results are compared with molecular dynamic simulation results. These results indicate that the HNC equation underestimates the main peak in S(k). When the Friedel oscillations are absent then MWC theory gives good results for S(k). But when Friedel oscillations are present then MWC equation reproduces simulation results beyond the main diffraction peak.     

Fourier representation method for electronic structures of linear polymers

The Fourier representation method described in the previous paper of this series is used to make electronic structure calculations for a linear chain of equally spaced hydrogen atoms. The electronic wavefunction is assumed to be a determinant of doubly-occupied crystal orbitals of modulated-plane-wave type, built from one 1s Slater-type orbital of screening parameter ζ centered on each atom. The energy is calculated from the electrostatic zero-order Hamiltonian with exact evaluation of all Coulomb and exchange contributions, and is optimized with respect to the lattice spacing and ζ value. Good agreement with work by others is noted, indicating a near-equivalence of modulated-plane-wave and tight-binding wavefunctions for this half-filled-valence-band system. The linear chain is calculated to be far more stable than cubic three-dimensional hydrogen crystals. This fact sheds light on the unusually large calculated nearest-neighbor distances in the cubic crystals, and is related to a suggestion that under certain conditions the most stable structure for solid atomic hydrogen may be of lower symmetry than cubic. The previous paper of this series: Harris, F. E.: J. Chem. Phys.56, 4422 (1972) [1]. Chargé de Recherches du F.N.R.S. (Fonds National Belge de la Recherche Scientifique).     

Analysis of Complex Mixtures of Aromatic Hydrocarbons. Relations between Retention Index and Molecular Structure

Abstract

Relationships between Kovats indices on nonpolar stationary phases and the structure of alkyl- and alkenylbenzenes, defined by the molecular connectivity or connectivity index, have been established.

Almost all components of aromatic naphthas are included in the different linear equations which relate both empirical indices. The constant terms of the straight lines depend on the nature and position of the substituents in the benzene ring. Substituents in para position do not influence each other, allowing the study of the effect of its nature on the ratio δI/Δχ

Equations for different series of compounds, including n-alkyl- and 1,4-di-n-alkylbenzene homologous series, are calculated in order to support its identification in aromatic naphthas.     

Combined QSAR-based virtual screening and fluorescence binding assay to identify natural product mediators of Interferon Regulatory Factor 7 (IRF-7) in pulmonary infection

Abstract

Interferon regulatory factor-7 (IRF-7) is involved in pulmonary infection and pneumonia. Here, a synthetic strategy that combined quantitative structure–activity relationship (QSAR)-based virtual screening and in vitro binding assay was described to identify new and potent mediator ligands of IRF-7 from natural products. In the procedure, a QSAR scoring function was developed and validated using Gaussian process (GP) regression and a structure-based set of protein–ligand affinity data. By integrating hotspot pocket prediction, pharmacokinetics profile analysis and molecular docking calculations, the scoring function was successfully applied to virtual screening against a large library of structurally diverse, drug-like natural products. With the method we were able to identify a number of potential hits, from which several compounds were found to have moderate or high affinity to IRF-7 using fluorescence binding assays, with dissociation constants K_d at micromolar level. We have also examined the structural basis and noncovalent interactions of computationally modelled IRF-7 complex with its potent ligands. It is revealed that hydrophobic forces and van der Waals contacts play a central role in stabilization of the complex architecture, while few hydrogen bonds confer additional specificity for the protein–ligand recognition.     

Theoretical investigation of the viscosity of some liquid metals and alloys

The viscosities of some liquid metals and liquid binary alloys have been determined using the theoretical model developed by Morioka et al. (Z. Metallkd. 93, 4 (2002)). The model was applied successfully to the liquid mono-component metals Hg and Na and to the liquid binary alloys Hg–Na, Ag–Cu, Bi–Sn and Ag–Sb. The model successfully described the temperature dependence of viscosity for Hg and Na for a wide range of temperatures. The values of the adjustable parameters k and z were obtained for Hg and Na. For the liquid binary alloys, calculations were done at a particular temperature for each alloy and our results show that for Hg–Na and Ag–Cu there are both qualitative and quantitative agreements between calculated and experimental viscosity data. However, Bi–Sn and Ag–Sb manifested significant levels of quantitative discrepancies between calculated and experimental viscosity data.     

Ab Initio and in-Crystal Geometry of trans-1,4-Dibromo1,4-dicarboxymethylcyclohexane

The structure of trans-1,4-dibromo-1,4-dicarboxymethylcyclohexane (I) has been determined by single crystal x-ray diffraction. The molecules, located on symmetry centers, are in the rigid chair conformation with the Br and COOCH₃ axial and equatorial, respectively. The molecular geometry observed in the crystal is similar to that calculated for the isolated molecule using ab initio calculations performed at the HF/6-31(d) level. A peculiar arrangement of the carboxymethyl substituents, along with short contacts involving the Br atoms, seem to play a role in the stabilization of the crystalline structure.     

Calculation of the ground‐state energy and studies of other properties of exotic helium atoms with the use of boundary conditions of wave function

The minimum energy and average distance between particles of doubly muonic helium atoms Heμμ (He²⁺ + 2μ ), are calculated with the use of a wave function that satisfies boundary conditions such as the behavior of the wave function when two particles are close to each other or far away from each other. In this wave function, the muon–muon correlation in doubly muonic helium atoms is described to arrive at the correct behavior for r₁₂ tending to zero and infinity. It is shown that the obtained results are very close to the values calculated by others. Finally, to confirm the method and results, calculated values are compared with a similar electronic system, and it is shown that the small differences in the energies of Heμμ and He are due to the reduced masses, as expected. In addition to being very simple, the proposed wave function provides relatively accurate values for the energy and expectation values of r²ⁿ, emphasizing the importance of the local properties of the wave functions. © 2004 Wiley Periodicals, Inc. Int J Quantum Chem, 2005     

Direct interchange reaction in a homopolymer melt. Evolution of the MWD: an analytical solution

Kinetics of a direct interchange reaction in a homopolymer melt is studied theoretically. Relaxation of the molecular weight distribution to its most probable (Flory) stationary form^[1] is considered. To this end, the time‐dependent generating function of the transient distribution is calculated analytically. Peculiarities of the relaxation process are investigated for two kinds of the initial distribution, namely, the sum of two Flory distributions with different number averages N₁ and N₁, and the delta‐function. The former case describes a blend of two polydisperse polymers whereas the latter corresponds to a monodisperse melt. In each case, the dependencies of the differential molecular weight distribution and the weight‐ and z‐average polymerization degrees on the number of interchanges per number average chain are obtained in the explicit form. Earlier studies of this problem are briefly discussed.