A statistical-mechanical theory of slow dynamics near the glass transition

A statistical-mechanical theory of slow dynamics near the glass transition in two kinds of glass-forming systems, (M) molecular systems and (S) suspensions of colloids, is presented from a unified point of view based on the Tokuyama-Mori projection operator method. The exact diffusion equations for the coherent- and the incoherent-intermediate scattering functions are first derived, whose memory functions are convolutionless in time and contain the correlation effects due to the hydrodynamic interactions in (S). The analytic expressions of the memory functions are then calculated within the mode-coupling theory (MCT) approximation and are shown to coincide with the conventional ones obtained by MCT. Alternative mode-coupling equations are thus obtained in (M) and (S) separately. Self-diffusion is also discussed. Alternative equations for the mean-square displacement and the non-Gaussian parameter are also derived within MCT approximation. All results in both the systems are compared with those obtained by MCT.     

Long time tails in stationary random media II: Applications

In a previous paper we developed a mode-coupling theory to describe the long time properties of diffusion in stationary, statistically homogeneous, random media. Here the general theory is applied to deterministic and stochastic Lorentz models and several hopping models. The mode-coupling theory predicts that the amplitudes of the long time tails for these systems are determined by spatial fluctuations in a coarse-grained diffusion coefficient and a coarse-grained free volume. For one-dimensional models these amplitudes can be evaluated, and the mode-coupling theory is shown to agree with exact solutions obtained for these models. For higher-dimensional Lorentz models the formal theory yields expressions which are difficult to evaluate. For these models we develop an approximation scheme based upon projecting fluctuations in the diffusion coefficient and free volume onto fluctuations in the density of scatterers.Work supported by grant No. CHE 77-16308 from the National Science Foundation and by a Nato Travel Grant.     

Renormalized field theory of critical dynamics

We formulate a Gell'Mann-Low-type renormalization group approach to the critical dynamics of stochastic models described by Langevin or Fokker-Planck equations including mode-coupling terms.Dynamical correlation and response functions are expressed in terms of path integrals, which are investigated by well-known methods of renormalized perturbation theory.Dynamical scaling laws and relations between static and dynamic critical exponents are derived. The leading temperature-dependence of correlation and response functions is obtained from the Kadanoff-Wilson short-distance expansion. We also consider corrections to dynamic scaling which are due to a finite lattice constant.     

模耦合理论计算纳米粒子在聚合物熔体中的含时扩散系数与常规扩散常数 (cited: 2)

分析和计算了纳米粒子在聚合物熔体中的含时扩散系数与常规扩散常数. 采用广义朗之万方程描述扩散动力学,并通过模耦合理论计算摩擦记忆内核.为简单起见,只考虑了来自两体碰撞和溶剂密度涨落耦合作用两类微观因素对摩擦记忆内核的贡献. 采用聚合物参考作用点模型以及Percus-Yevick闭合条件计算了聚合物-纳米粒子复合溶液的平衡态结构信息函数;详尽分析了纳米粒子的尺寸与聚合物链的尺寸对扩散动力学的影响. 揭示了结构函数、摩擦记忆内核以及扩散系数等随着纳米粒子半径和聚合物链长的变化关系. 结果表明,对于小尺寸的纳米粒子或者短链的聚合物,短时间的非马尔可夫扩散 动力学特征比较显著,含时扩散系数需要更长的时间弛豫到常规扩散常数. 微观因素对扩散常数的贡献随着纳米粒子尺寸的增加而减小,却随着聚合物链长的增加而增大. 此外,模耦合理论得到的扩散常数与Stokes-Einstein关系的预测值进行比较,发现对于小尺寸的纳米粒子或者长链的聚合物,微观因素对扩散常数的的贡献占主导地位. 相反,当纳米粒子较大或者聚合物链长较短时,流体力学的贡献会发挥重要作用.     

Dynamic properties,scaling and related freezing criteria of two- and three-dimensional colloidal dispersions

The static and dynamic properties of 2- and 3-dimensional dispersions of strongly interacting colloidal spheres are examined. Quasi-2-dimensional dispersions of particles interacting by long range electrostatic and dipolar magnetic forces, respectively, are investigated using Brownian dynamics computer simulations with hydrodynamic interactions included. The dynamics of 3-dimensional bulk dispersions of charge-stabilized and neutral colloidal spheres is determined from a fully self-consistent mode-coupling scheme. For systems with long range repulsive interactions the dynamic correlation functions are shown to obey dynamic scaling in terms of a characteristic relaxation time related to the mean particle distance. Hydrodynamic interactions introduce a second characteristic length scale, and they lead to more restricted scaling behaviour with an enhancement of self-diffusion and, for 2-dimensional systems, to the divergence of the short-time collective diffusion coefficient. As a consequence of dynamic scaling, a dynamic criterion for the onset of colloidal freezing related to long-time self-diffusion is shown to be equivalent to a static freezing criterion related to the 2- and 3-dimensional static structure factors. Alternative freezing criteria are given in terms of the long-time and the mean collective diffusion coefficients.     

Quantum statistical effects in nuclear reactions,fission, and open quantum systems

Quantum diffusion equations with time-dependent transport coefficients are derived from generalized non-Markovian Langevin equations. Generalized fluctuation-dissipation relations and analytical formulas for calculating friction and diffusion coefficients in nuclear processes are obtained. The asymptotics of the transport coefficients and of the correlation functions are investigated. The problem of correlation decay in quantum dissipative systems is studied. A comparative analysis of diffusion coefficients for the harmonic and inverted oscillators is performed. The role of quantum statistical effects during passage through a parabolic potential barrier is investigated. Sets of diffusion coefficient assuring the purity of states at any time instant are found in cases of non-Markovian dynamics. The influence of different sets of transport coefficients on the rate of decay from a metastable state is studied in the framework of the master equation for reduced density matrices describing open quantum systems. The approach developed is applied to investigation of fission processes and the processes of projectile-nuclei capture by target nuclei for bombarding energies in the vicinity of the Coulomb barrier. The influence of dissipation and fluctuation on these processes is taken into account in a self-consistent way. The evaporation residue cross sections for asymmetric fusion reactions are calculated from the derived capture probabilities averaged over all orientations of the deformed projectile and target nuclei.     

Quantum non-Markovian Langevin equations and transport coefficients

Quantum diffusion equations featuring explicitly time-dependent transport coefficients are derived from generalized non-Markovian Langevin equations. Generalized fluctuation-dissipation relations and analytic expressions for calculating the friction and diffusion coefficients in nuclear processes are obtained. The asymptotic behavior of the transport coefficients and correlation functions for a damped harmonic oscillator that is linearly coupled in momentum to a heat bath is studied. The coupling to a heat bath in momentum is responsible for the appearance of the diffusion coefficient in coordinate. The problem of regression of correlations in quantum dissipative systems is analyzed.     

High-order mode-coupling theory for the colloidal glass transition

A theoretical approach is developed to derive a hierarchy of mode-coupling equations for the dynamics of concentrated colloidal suspensions, which improves the prediction of the colloidal glass transition. Our derivation is based on a matrix formalism for stochastic dynamics and the resulting recursive expressions for irreducible memory functions. The 1st order truncation of the generalized mode-coupling closure recovers mode-coupling theory, whereas its 2nd and 3rd order truncations provide corrections. The predictions of the transition volume fraction and Debye-Waller parameter for the hard-sphere colloidal system improve with the increasing mode-coupling order and compare favorably with experimental measurements.     

A theoretical model for the collective motion of proteins by means of principal component analysis

A coarse grained model in the frame work of principal component analysis is presented. We used a bath of harmonic oscillators approach, based on classical mechanics, to derive the generalized Langevin equations of motion for the collective coordinates. The dynamics of the protein collective coordinates derived from molecular dynamics simulations have been studied for the Bovine Pancreatic Trypsin Inhibitor. We analyzed the stability of the method by studying structural fluctuations of the C _a atoms obtained from a 20 ns molecular dynamics simulation. Subsequently, the dynamics of the collective coordinates of protein were characterized by calculating the dynamical friction coefficient and diffusion coefficients along with time-dependent correlation functions of collective coordinates. A dual diffusion behavior was observed with a fast relaxation time of short diffusion regime 0.2–0.4 ps and slow relaxation time of long diffusion about 1–2 ps. In addition, we observed a power law decay of dynamical friction coefficient with exponent for the first five collective coordinates varying from −0.746 to −0.938 for the real part and from −0.528 to −0.665 for its magnitude. It was found that only the first ten collective coordinates are responsible for configuration transitions occurring on time scale longer than 50 ps.     

Langevin dynamics of the glass forming polymer melt: Fluctuations around the random phase approximation

In this paper the Martin-Siggia-Rose (MSR) functional integral representation is used for the study of the Langevin dynamics of a polymer melt in terms of collective variables: mass density and response field density. The resulting generating functional (GF) takes into account fluctuations around the random phase approximation (RPA) up to an arbitrary order. The set of equations for the correlation and response functions is derived. It is generally shown that for cases whenever the fluctuation-dissipation theorem (FDT) holds we arrive at equations similar to those derived by Mori-Zwanzig. The case when FDT in the glassy phase is violated is also qualitatively considered and it is shown that this results in a smearing out of the ideal glass transition. The memory kernel is specified for the ideal glass transition as a sum of all “water-melon” diagrams. For the Gaussian chain model the explicit expression for the memory kernel was obtained and discussed in a qualitative link to the mode-coupling equation. Received: 9 January 1998 / Revised: 24 April 1998 / Accepted: 2 July 1998     

Colloidal glass transition: beyond mode-coupling theory

A new theory for the dynamics of concentrated colloidal suspensions and the colloidal glass transition is proposed. The starting point is the memory function representation of the density correlation function. The memory function can be expressed in terms of a time-dependent pair-density correlation function. An exact, formal equation of motion for this function is derived and a factorization approximation is applied to its evolution operator. In this way a closed set of equations for the density correlation function and the memory function is obtained. The theory predicts an ergodicity breaking transition similar to that predicted by mode-coupling theory, but at a higher density.     

Short-time correlations of many-body systems described by nonlinear Fokker–Planck equations and Vlasov–Fokker–Planck equations

Analytical expressions for short-time correlation functions, diffusion coefficients, mean square displacement, and second order statistics of many-body systems are derived using a mean field approach in terms of nonlinear Fokker–Planck equations and Vlasov–Fokker–Planck equations. The results are illustrated for the Desai–Zwanzig model, the nonlinear diffusion equation related to the Tsallis statistics, and a Vlasov–Fokker–Planck equation describing bunch particles in particle accelerator storage rings.     

Scaling behavior in the dynamics of a supercooled Lennard-Jones mixture

Summary We present the results of a large-scale molecular-dynamics computer simulation of a binary, supercooled Lennard-Jones fluid. At low temperatures and intermediate times the time dependence of the intermediate scattering function is well described by a von Schweidler law. The von Schweidler exponent is independent of temperature and depends only weakly on the type of correlator. For long times the correlation functions show a Kohlrausch behavior with an exponent β that is independent of temperature. This dynamical behavior is in accordance with the mode-coupling theory of supercooled liquids. Paper presented at the I International Conference on Scaling Concepts and Complex Fluids, Copanello, Italy, July 4–8, 1994.     

Long time tails in stationary random media. I. Theory

Diffusion of moving particles in stationary disordered media is studied using a phenomenological mode-coupling theory. The presence of disorder leads to a generalized diffusion equation, with memory kernels having power law long time tails. The velocity autocorrelation function is found to decay like t^–(d/2+1), while the time correlation function associated with the super-Burnett coefficient decays liket ^–d/2 for long times. The theory is applicable to a wide variety of dynamical and stochastic systems including the Lorentz gas and hopping models. We find new, general expressions for the coefficients of the long time tails which agree with previous results for exactly solvable hopping models and with the low-density results obtained for the Lorentz gas. Finally we mention that if the moving particles are charged, then the long time tails imply that there is an ^d/2 contribution to the low-frequency part of the frequency-dependent electrical conductivity.     

Analytical solutions of the simplified spherical harmonics equations

We derived analytical solutions of the simplified spherical harmonics equations, an approximation of the radiative transfer equation, for infinitely extended scattering media. The derived equations are simple (sum of exponential functions) and quickly evaluated. We compared the solutions with Monte Carlo simulations in the steady-state and time domains and found much better agreement compared to solutions of the diffusion equation, especially for large absorption coefficients, short time values, and small distances from the source.     

Upper critical dimension, dynamic exponent, and scaling functions in the mode-coupling theory for the Kardar-Parisi-Zhang equation

We study the mode-coupling approximation for the Kardar-Parisi-Zhang equation in the strong-coupling regime. By constructing an ansatz consistent with the asymptotic forms of the correlation and response functions we determine the upper critical dimension d(c) = 4 and the expansion z = 2-(d-4)/4+O((4-d)2) around dc. We find the exact z = 3/2 value in d = 1, and estimate the values z approximately 1.62, z approximately 1.78 in d = 2, 3. The result dc = 4 and the expansion around dc are very robust and can be derived just from a mild assumption on the relative scale on which the response and correlation functions vary as z approaches 2.     

Dielectric and transport properties of a supercooled symmetrical molten salt

The liquid-glass transition of the restricted primitive model for a symmetrical molten salt is studied using mode-coupling theory. The transition at high densities is predicted to obey the Lindemann criterion for melting, and the charge-density peak found in neutron-scattering experiments on ionic glass formers is qualitatively reproduced. Frequency-dependent dielectric functions, shear viscosities, and dynamical conductivities of the supercooled liquid are presented. Comparing the latter to the diffusion constant, we find that mode-coupling theory reproduces the Nernst-Einstein relation. The Stokes-Einstein radius is found to be approximately equal to the particle radius only near the high-density glass transition.     

Hydrodynamics and time correlation functions for cellular automata

Hydrodynamic excitations in lattice gas cellular automata are described in terms of equilibrium time correlation functions for the local conserved variables. For large space and time scales the linearized hydrodynamic equations are obtained to Navier-Stokes order. Exact expressions for the associated susceptibilities and transport coefficients are identified in terms of correlation functions. The general form of the time correlation functions for conserved densities in the hydrodynamic limit is given and illustrated by some examples suitable for comparison with computer simulation. The transport coefficients are related to time correlation functions for the conserved fluxes in a way analogous to the Green-Kubo expressions for continuous fluids. The general results are applied for a one-component fluid and several types of binary diffusion. Also discussed are the effects of unphysical slow modes such as staggered particle or momentum densities.     

The long time and Brownian limits for tagged particle motion in liquids

Formally exact theories of tagged particle motion in liquids are developed, based upon kinetic theory for hard spheres and mode coupling for smooth potentials. It is shown that the resulting equations are tractable in the long time and Brownian limits. The coefficient of the long time tail of the velocity correlation function is seen to differ from its low-density form by only the replacement of the low-density viscosity and diffusion constant by the true viscosity and diffusion constant. In the Brownian limit, the slip Stokes-Einstein law is obtained, with the true viscosity. The relation to other work is discussed.Supported by NSF Grant No. CHE81-11422 and by a Dreyfus Teacher-Scholar grant to TK.     

Extensions of the field-emission fluctuation method for the determination of surface diffusion coefficients

The use of scanning tunneling microscopy and related techniques for the determination of surface diffusion coefficients of adsorbates is discussed. Three schemes, all extensions of the field-emission current fluctuation method are presented and analyzed. The first consists of determining single site correlation functions with a STM in its more or less normal operating mode. The second consists of retracting the tip approximately one tip radius so that a circular region of high field is created on the flat surface from which field emission and diffusion-induced current fluctuations can be obtained. The third considers creation of a long narrow region of high field by placing a very fine cylindrical wire parallel to and above the plane substrate. This last scheme allows determination of diffusion anisotropy. Detailed expressions for the current correlation functions for the three schemes and criteria for allowed vibrational amplitudes and drift are derived. It is concluded that all three schemes should be feasible but probably would differ in the range of diffusion coefficient values they would be able to handle.