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81.
A self-consistent mode-coupling theory is presented for the viscosity of solutions of charged rodlike polymers. The static structure factor used in the theory is obtained from polymer integral equation theory; the Debye-Huckel approximation is inadequate even at low concentrations. The theory predicts a nonmonotonic dependence of the reduced excess viscosity eta(R) on concentration from the behavior of the static structure factor in polyelectrolyte solutions. The theory predicts that the peak in eta(R) occurs at concentrations slightly lower than the overlap threshold concentration, c*. The peak height increases dramatically with increasing molecular weight and decreases with increased concentrations of added salt. The position of the peak, as a function of concentration divided by c*, is independent of salt concentration or molecular weight. The predictions can be tested experimentally. 相似文献
82.
Thermolysis of an in situ generated intermediate, produced from the reaction of [Cp*MoCl(4)] (Cp* = η(5)-C(5)Me(5)) and [LiBH(4).THF], with excess Te powder yielded isomeric [(Cp*Mo)(2)B(4)TeH(5)Cl] (2 and 3), [(Cp*Mo)(2)B(4)(μ(3)-OEt)TeH(3)Cl] (4), and [(Cp*Mo)(4)B(4)H(4)(μ(4)-BH)(3)] (5). Cluster 4 is a notable example of a dimolybdaoxatelluraborane cluster where both oxygen and tellurium are contiguously bound to molybdenum and boron. Cluster 5 represents an unprecedented metal-rich metallaborane cluster with a cubane core. The dimolybdaheteroborane 2 was found to be very reactive toward metal carbonyl compounds, and as a result, mild pyrolysis of 2 with [Fe(2)(CO)(9)] yielded distorted cubane cluster [(Cp*Mo)(2)(BH)(4)(μ(3)-Te){Fe(CO)(3)}] (6) and with [Co(2)(CO)(8)] produced the bicapped pentagonal bipyramid [(Cp*MoCo)(2)B(3)H(2)(μ(3)-Te)(μ-CO){Co(3)(CO)(6)}] (7) and pentacapped trigonal prism [(Cp*MoCo)(2)B(3)H(2)(μ(3)-Te)(μ-CO)(4){Co(6)(CO)(8)}] (8). The geometry of 8 is an example of a heterometallic boride cluster in which five Co and one Mo atom define a trigonal prismatic framework. The resultant trigonal prism core is in turn capped by two boron, one Te, and one Co atom. In the pentacapped trigonal prism unit of 8, one of the boron atoms is completely encapsulated and bonded to one molybdenum, one boron, and five cobalt atoms. All the new compounds have been characterized in solution by IR, (1)H, (11)B, and (13)C NMR spectroscopy, and the structural types were unambiguously established by crystallographic analysis of 2 and 4-8. 相似文献
83.
Layer-wise, distance-dependent orientational relaxation of water confined in reverse micelles (RM) is studied using theoretical and computational tools. We use both a newly constructed "spins on a ring" (SOR) Ising-type model (with Shore-Zwanzig rotational dynamics) and atomistic simulations with explicit water. Our study explores the effect of reverse micelle size and role of intermolecular correlations, compromised by the presence of a highly polar surface, on the distance (from the interface) dependence of water relaxation. The "spins on a ring" model can capture some aspects of distance dependence of relaxation, such as acceleration of orientational relaxation at intermediate layers. In atomistic simulations, layer-wise decomposition of hydrogen bond formation pattern clearly reveals that hydrogen bond arrangement of water at a certain distance away from the surface can remain frustrated due to the interaction with the polar surface head groups. This layer-wise analysis also reveals the presence of a non-monotonic slow relaxation component which can be attributed to this frustration effect and which is accentuated in small to intermediate size RMs. For large size RMs, the long time component decreases monotonically from the interface to the interior of the RMs with slowest relaxation observed at the interface. 相似文献
84.
Dielectric relaxation in orientationally disordered dipolar solids often exhibits exotic features, such as a strong Cole-Cole relaxation for simple molecular solids. However, there does not seem to exist a detailed molecular theory of such phenomena. In this article, a molecular hydrodynamic theory of dielectric relaxation in solid rotator phases, such as plastic crystals, is presented. 相似文献
85.
S.N. Bagchi 《物理学进展》2013,62(77):119-173
An expression for the intensity function scattered coherently by an arbitrarily distorted lattice has been derived which degenerates under well-defined conditions to the well-known formulae valid for crystals, liquids and gases or amorphous substances. A new method for the analysis of the radial distribution function (RDF) of simple liquids has been suggested. RDF curves for liquid argon near the triple point have been analysed to obtain the distance statistics of neighbours and their coordination numbers. Using the first-neighbour statistics an expression for the partition function for matter of any kind and, in particular, for simple liquids has been deduced. 相似文献
86.
Deformations of the canonical commutation relations lead to non-Hermitian momentum and position operators and therefore almost inevitably to non-Hermitian Hamiltonians. We demonstrate that such type of deformed quantum mechanical systems may be treated in a similar framework as quasi/pseudo and/or -symmetric systems, which have recently attracted much attention. For a newly proposed deformation of exponential type we compute the minimal uncertainty and minimal length, which are essential in almost all approaches to quantum gravity. 相似文献
87.
Manjari Bagchi Jishnu Dey Mira Dey Taparati Gangopadhyay Sibasish Laha Subharthi Ray Monika Sinha 《Physics letters. [Part B]》2008
High energy density (?) and temperature (T) links general relativity and hydrodynamics leading to a lower bound for the ratio of shear viscosity (η) and entropy density (s ). We get the interesting result that the bound is saturated in the simple model for quark matter that we use for strange stars at the surface for T∼80 MeV. At this T we have the possibility of cosmic separation of phases. At the surface of the star where the pressure is zero—the density ? has a fixed value for all stars of various masses with correspondingly varying central energy density ?c. Inside the star where this density is higher, the ratio of η/s is larger and are like the known results found for perturbative QCD. This serves as a check of our calculation. The deconfined quarks at the surface of the strange star at T=80 MeV seem to constitute the most perfect interacting fluid permitted by nature. 相似文献
88.
Biman Bagchi 《Molecular physics》2014,112(9-10):1418-1426
Several time dependent fluorescence Stokes shift (TDFSS) experiments have reported a slow power law decay in the hydration dynamics of a DNA molecule. Such a power law has neither been observed in computer simulations nor in some other TDFSS experiments. Here we observe that a slow decay may originate from collective ion contribution because in experiments DNA is immersed in a buffer solution, and also from groove bound water and lastly from DNA dynamics itself. In this work we first express the solvation time correlation function in terms of dynamic structure factors of the solution. We use mode coupling theory to calculate analytically the time dependence of collective ionic contribution. A power law decay in seen to originate from an interplay between long-range probe–ion direct correlation function and ion–ion dynamic structure factor. Although the power law decay is reminiscent of Debye–Falkenhagen effect, yet solvation dynamics is dominated by ion atmosphere relaxation times at longer length scales (small wave number) than in electrolyte friction. We further discuss why this power law may not originate from water motions which have been computed by molecular dynamics simulations. Finally, we propose several experiments to check the prediction of the present theoretical work. 相似文献
89.
Densification of powder compacts during sintering (initial stage) under constant heating rate has been studied and methods of analysing the densification kinetic data have been suggested. p]Green compacts can broadly be envisaged to consists of two phases, viz. porosity and solid material. Annihilation of the pores causes densification of the compacts during sintering. So, the kinetics of the initial stage of densification may very well be represented by a densification parameter (α),where Here, vs and vp,respectively, denote the pore volumes of the sintered and the green compact. Continuous and in situ recording of the linear shrinkage (ΔL) of the compacts during the sintering may be done with a dilatometer and using this value of ΔL,the value of α at any temperature (T) may be calculated.These kinetic data (α vs. T)may then be subjected to analysis using the well-known methods of thermal analysis, and the so-called “derived activation energy (E)” of densification may be evaluated therefrom. The exact form of g(α)—governing rate equation—is ascertained by a trial-and-error method.These methods were used to analyse the densification kinetic data of haematite, copper and silver powders (with particles of irregular shapes and sizes). The results of such analyses will appear on other parts of this paper. 相似文献
90.