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Some fluids are known to behave anomalously. The so-called structural anomaly which means that the fluid becomes less structures under isothermal compression is among the most frequently discussed ones. Several methods for quantifying the degree of structural order are described in the literature and are used for calculating the region of structural anomaly. It is generally thought that all of the structural order determinations yield qualitatively identical results. However, no explicit comparison was made. This paper presents such a comparison for the first time. The results of some definitions are shown to contradict the intuitive notion of a fluid. On the basis of this comparison, we show that the region of structural anomaly can be most reliably determined from the behavior of the excess entropy. [ABSTRACT FROM AUTHOR]

Smoothed dissipative particle dynamics (SDPD) is a novel coarse grained method for the numerical simulation of complex fluids. It has considerable advantages over more traditional particle-based methods. In this paper we analyze the self-diffusion coefficient D of a SDPD solvent by using the strategy proposed by Groot and Warren [J. Chem. Phys. 107, 4423 (1997)]. An analytical expression for D in terms of the model parameters is developed and verified by numerical simulations. [ABSTRACT FROM AUTHOR]

For an isolated resonance of an isolated chromophore in a condensed phase, the absorption line shape is often more sharply peaked than the distribution of transition frequencies as a result of motional narrowing. The latter arises from the time-dependent fluctuations of the transition frequencies. It is well known that one can incorporate these dynamical effects into line shape calculations within a semiclassical approach. For a system of coupled chromophores, both the transition frequencies and the interchromophore couplings fluctuate in time. In principle one can again solve this more complicated problem with a related semiclassical approach, but in practice, for large numbers of chromophores, the computational demands are prohibitive. This has led to the development of a number of approximate theoretical approaches to this problem. In this paper we develop another such approach, using a time-averaging approximation. The idea is that, for a single chromophore, a motionally narrowed line shape can be thought of as a distribution of time-averaged frequencies. This idea is developed and tested on both stochastic and more realistic models of isolated chromophores, and also on realistic models of coupled chromophores, and it is found that in all cases this approximation is quite satisfactory, without undue computational demands. This approach should find application for the vibrational spectroscopy of neat liquids, and also for proteins and other complicated multichromophore systems. [ABSTRACT FROM AUTHOR]

Classical molecular dynamics simulations are carried out between 190 and 250 K on an ultrathin ice film doped by HCl deposition with a coverage varying from 0.3 to 1.0 monolayer. These conditions are similar to those defined in the experiments described in the companion paper. Within the assumption that the hydracid molecule remains in its molecular form, the order parameters and the diffusion coefficients for the H[sub 2]O molecules are determined in the HCl doped ice film, and compared to the experimental data. The residence times of HC1 at the ice surface are also calculated. Below 200 K, the HC1 molecules are found to remain localized at the ice surface, while above 200 K, the HC1 diffusion inside the film is easy and leads to a strong disorder of the ice structure. Although the formation of hydrates cannot be interpreted by the present calculations, the lowering of the ice melting temperature by 15 K measured in neutron experiments for an HC1 doped ice film is qualitatively explained by simulation results. [ABSTRACT FROM AUTHOR]

The presence of space charge in the polymeric insulation of high-voltage cables is thought to be correlated with electric breakdown. However, a direct link between molecular properties, space charge formation and eventual breakdown has still to be established. It is clear that both physical (e.g., conformational disorder) and chemical defects (e.g., broken bonds and impurities) are present in insulating materials and that both may trap electrons. We have shown that by defining the defect energy in terms of the molecular electron affinity, a relationship is established between the electron trap and the molecular properties of the material. In a recent paper [M. Meunier and N. Quirke, J. Chem. Phys. 113, 369 (2000)] we proposed methods that have made it possible to provide estimates of the energy, number and residence times of electrons in conformational traps in polyethylene. Typical physical trap energies are of the order of 0.15 eV and all are less than 0.3 eV. In the present paper we focus on the role of chemical defects, where we expect much deeper traps but at very low concentrations. Following the methodology used in our previous paper we have used density-functional theory to calculate trap energies for a set of chemical impurities and additives commonly found in polyethylene used for high-voltage cable insulation. In an extension of our approach we have estimated the effect of neighboring molecules on the trap energies of such defects. The resulting trap energy-trap density distribution reveals some very deep (>1 eV) traps presumably implicated in the formation of long-lived space charge in polymeric insulators and consequently to changes in the dielectric properties of the material. © 2001 American Institute of Physics. [ABSTRACT FROM AUTHOR]

A central issue in the study of polymer physics is to understand the relation between the geometrical properties of macromolecules and various dynamics, most of which are encoded in the Laplacian spectra of a related graph describing the macrostructural structure. In this paper, we introduce a family of treelike polymer networks with a parameter, which has the same size as the Vicsek fractals modeling regular hyperbranched polymers. We study some relevant properties of the networks and show that they have an exponentially decaying degree distribution and exhibit the small-world behavior. We then study the Laplacian eigenvalues and their corresponding eigenvectors of the networks under consideration, with both quantities being determined through the recursive relations deduced from the network structure. Using the obtained recursive relations we can find all the eigenvalues and eigenvectors for the networks with any size. Finally, as some applications, we use the eigenvalues to study analytically or semi-analytically three dynamical processes occurring in the networks, including random walks, relaxation dynamics in the framework of generalized Gaussian structure, as well as the fluorescence depolarization under quasiresonant energy transfer. Moreover, we compare the results with those corresponding to Vicsek fractals, and show that the dynamics differ greatly for the two network families, which thus enables us to distinguish between them. [ABSTRACT FROM AUTHOR]

Structure of fluids is suitably characterized by distribution functions from which the most important is the pair correlation function. Theoretical approaches to get the pair distribution function are based mainly on the solution of the Ornstein–Zernike (OZ) integral equation. In this paper, the OZ equation for molecular fluids is modified to yield the average correlation function for systems of convex molecules. In our approach we employed the previously proposed method to separate the shape effect of molecular cores from that due to the variable surface–surface distances among three pairs of convex cores. The effect of nonspherical shape of hard cores in the convolution integral is expressed through the derivative with respect to three surface–surface distances of the expression for the hard convex body third virial coefficient. For simple fluids (with the pointwise cores) the derived expression reduces to the standard OZ equation. The modified OZ equation is solved numerically for the Percus–Yevick-type closure and the average correlation functions in the systems of hard spherocylinders with l/σ=0.4, 0,6 and 1 were determined. The obtained dependencies of the average correlation functions on the reduced distances calculated from the modified OZ equation agree well with the simulation data for the above systems at relatively high densities. © 2001 American Institute of Physics. [ABSTRACT FROM AUTHOR]

The jet-cooled FTIR spectrum of the ν[sub 6] fundamental band (C-O stretch) of vanadium hexacarbonyl, V(CO)[sub 6], is studied for the first time. The spectrum shows a very unusual structure consisting of three well-defined broad subbands, without the usual PQR structure. V(CO)[sub 6] being an open-shell system this is attributed to a dynamical F[sub 2g]xF[sub 1u] Jahn-Teller coupling which considerably complicates the analysis. A new theoretical model based on group theory and tensorial algebraic techniques is developed in this paper for the very first attempt to analyze such a rovibronic spectrum. The assumption of a negligible spin-orbit coupling is validated by the overall agreement between predicted and observed band profiles. The rovibronic Hamiltonian and dipole moment operators have been expanded in order to enable a simultaneous treatment of the four vibronic sublevels. We were able to satisfactorily reproduce the band profile and thus to give the first estimation of some rovibronic parameters for this molecule. © 2001 American Institute of Physics. [ABSTRACT FROM AUTHOR]