Extended Abstract: Glass forming organic liquids and polymers exhibit long range density fluctuations with correlation length ξ in the range of 10–300 nm at temperatures above Tg (1 - 6). This follows from dynamic and static light scattering experiments revealing some unexpected features, which cannot be explained on the basis of conventional liquid state theories: (i) In static light scattering the intensity I(q → 0) is no longer proportional to the isothermal compressibility, (ii) This excess scattering Iexc shows a strong q-dependence (q = (4π/Λ.)sin(θ/2)) corresponding to a correlation length ξ in the above mentioned range, (iii) The Landau-Placzek ratio IRayleigh/2IBrillouin is much too high compared with the results of light scattering theories, (iv) In photon correlation spectroscopy a new ultraslow hydrodynamic mode (Γ ˜ q2) is detected with relaxation rates Γ about 10−6 to 10−9 lower than those of the α-process at a given temperature. In order to explain these observations, a two-state fluid model is proposed, which starts from the coexistence of “liquid-like” and “aperiodic solid-like” regions within the liquids. Such ideas have been discussed many times before, so for example A.R. Ubbelohde (7) speculates about “anticrystalline” clusters in liquids. Molecular dynamics simulations of atomic liquids showed that long range orientational fluctuations appear upon supercooling (8). A preferred icosahedral ordering is observed (9) and the number of icosahedral clusters increases with decreasing temperature (10). In connection with the interpretation of the dynamics of supercooled liquids different “two-state” models have been proposed (11 - 15). For the explanation of the light scattering results we propose that the molecules in the different dynamic states (“liquid” or “solid”) aggregate during annealing of the liquid at temperatures above Tg. Experiments showed that the equilibration times can be rather long (3 - 5), but nevertheless the liquids exhibiting long range density fluctuations are in the state of lowest free energy. We claim that our observations are the first experimental proof of the existence of such different dynamic states, which have been discussed many times before. The extended secondary clusters can also be detected by ultra small angle X-ray scattering. 相似文献
This work presents the findings of a study to quantify the relative effectiveness of the primer preseating operation in small caliber cartridge production. In theory, primer preseating would enable cartridge stamping tools to achieve deeper stamping penetration depths and subsequently, greater primer retention forces. This is because, with preseating incorporated in the existing small caliber cartridge production process, a cartridge stamping tool would be fully dedicated to performing the case stamping operation (rather than the simultaneous primer seating and case stamping operations it currently performs). The findings presented in this work include measured percentages of total stamping tool force dedicated to primer seating, stamping tool penetration depths with and without primer preseating and primer retention forces with and without primer preseating. These findings and their underlying principles were produced through a static force equilibrium analysis and finite element modeling and simulation studies. 相似文献
In a granular gas of rough particles the spin of a grain is correlated with its linear velocity. We develop an analytical
theory to account for these correlations and compare its predictions to numerical simulations, using Direct Simulation Monte
Carlo as well as Molecular Dynamics. The system is shown to relax from an arbitrary initial state to a steady-state, which
is characterized by time-independent, finite correlations of spin and linear velocity. The latter are analyzed systematically
for a wide range of system parameters, including the coefficients of tangential and normal restitution as well as the moment
of inertia of the particles. For most parameter values the axis of rotation and the direction of linear momentum are perpendicular
like in a sliced tennis ball, while parallel orientation, like in a rifled bullet, occurs only for a small range of parameters.
The limit of smooth spheres is singular: any arbitrarily small roughness unavoidably causes significant translation-rotation
correlations, whereas for perfectly smooth spheres the rotational degrees of freedom are completely decoupled from the dynamic
evolution of the gas. 相似文献
Hydroxy‐mediated methoxy formation or stabilization is probably an important process in many methanol adsorption systems. Hydrogen atoms originating from the scission of the methanol O? H bond react with the substrate and form water. This process may result 1) in the production of additional surface defects as reactive centers for methoxy formation and 2) in the stabilization of methoxy groups by suppression of methanol formation.
Total intermolecular interaction energies are determined with a first version of the Gaussian electrostatic model (GEM-0), a force field based on a density fitting approach using s-type Gaussian functions. The total interaction energy is computed in the spirit of the sum of interacting fragment ab initio (SIBFA) force field by separately evaluating each one of its components: electrostatic (Coulomb), exchange repulsion, polarization, and charge transfer intermolecular interaction energies, in order to reproduce reference constrained space orbital variation (CSOV) energy decomposition calculations at the B3LYP/aug-cc-pVTZ level. The use of an auxiliary basis set restricted to spherical Gaussian functions facilitates the rotation of the fitted densities of rigid fragments and enables a fast and accurate density fitting evaluation of Coulomb and exchange-repulsion energy, the latter using the overlap model introduced by Wheatley and Price [Mol. Phys. 69, 50718 (1990)]. The SIBFA energy scheme for polarization and charge transfer has been implemented using the electric fields and electrostatic potentials generated by the fitted densities. GEM-0 has been tested on ten stationary points of the water dimer potential energy surface and on three water clusters (n = 16,20,64). The results show very good agreement with density functional theory calculations, reproducing the individual CSOV energy contributions for a given interaction as well as the B3LYP total interaction energies with errors below kBT at room temperature. Preliminary results for Coulomb and exchange-repulsion energies of metal cation complexes and coupled cluster singles doubles electron densities are discussed. 相似文献
The Doppler-free laser-spectroscopic frequency measurement of Doppler-shifted optical lines in forward and backward direction
of a fast ion beam permits a sensitive test of the relativistic Doppler-formula and, hence, the relativistic time dilation
factor . An experiment on metastable 7Li+, stored at a velocity of v = 0.064c in the Heidelberg heavy-ion storage ring TSR, has confirmed time dilation with unprecedented accuracy. Latest tests at two
different ion-velocities (v = 0.03c and v = 0.064c) will enhance these measurements. An improved version of this experiment will be carried out at the experimental storage
ring (ESR) at the Gesellschaft für Schwerionenforschung (GSI) in Darmstadt. The ESR permits 7Li+ to be stored at v = 0.33c which promises an improvement of the sensitivity to deviations from γSR by an order of magnitude. A first test at the ESR has shown the feasibility for this kind of experiment. 相似文献
Hard or abrupt glottal attack (HGA) is one of the vocal behaviors often associated with benign lesion of the vocal folds. This study was designed to determine whether the frequency of HGA was different in hyperfunctional voice patients with and without vocal fold masses. One hundred and forty-seven subjects were studied. All subjects received a complete otolaryngological evaluation including strobovideolaryngoscopy, objective voice measures, and evaluation by a speech-language pathologist. Thirty-two patients were diagnosed with muscle tension dysphonia (19 male, 13 female) without vocal fold masses. Fifty-seven patients were diagnosed with unilateral vocal fold masses (29 male, 28 female), most of which were cysts. Fifty-eight patients were diagnosed with bilateral vocal fold masses (13 male, 45 female). Of the 45 females with bilateral vocal fold masses. 26 had a vocal cyst and reactive nodule and 19 had bilateral vocal fold nodules. The control group was balanced and matched based on sex and on percentage of singers and nonsingers. It consisted of 49 subjects with no vocal fold pathology (20 male, 29 female). The group was composed of professional speakers, singers, and nonprofessional speakers. All voice disordered groups demonstrated higher frequencies of HGA than the control group. Differences were found between the male and female subjects in this study. No differences were found between the various disorders. Differences were also found between the subgroups of bilateral masses, where the bilateral nodules group presented a higher frequency of HGA than the cyst and contralateral reactive nodule. 相似文献
In this paper we introduce a computational method for proving the existence of generic saddle-to-saddle connections between equilibria of first order vector fields. The first step consists of rigorously computing high order parametrizations of the local stable and unstable manifolds. If the local manifolds intersect, the Newton–Kantorovich theorem is applied to validate the existence of a so-called short connecting orbit. If the local manifolds do not intersect, a boundary value problem with boundary values in the local manifolds is rigorously solved by a contraction mapping argument on a ball centered at the numerical solution, yielding the existence of a so-called long connecting orbit. In both cases our argument yields transversality of the corresponding intersection of the manifolds. The method is applied to the Lorenz equations, where a study of a pitchfork bifurcation with saddle-to-saddle stability is done and where several proofs of existence of short and long connections are obtained. 相似文献