Energy diffusion controlled reaction rate in dissipative Hamiltonian systems

In this paper the energy diffusion controlled reaction rate in dissipative Hamiltonian systems is investigated by using the stochastic averaging method for quasi Hamiltonian systems. The boundary value problem of mean first-passage time (MFPT) of averaged system is formulated and the energy diffusion controlled reaction rate is obtained as the inverse of MFPT. The energy diffusion controlled reaction rate in the classical Kramers bistable potential and in a two-dimensional bistable potential with a heat bath are obtained by using the proposed approach respectively. The obtained results are then compared with those from Monte Carlo simulation of original systems and from the classical Kramers theory. It is shown that the reaction rate obtained by using the proposed approach agrees well with that from Monte Carlo simulation and is more accurate than the classical Kramers rate.     

Projector formalism of generalized Brownian motion theory applied to dissipative and noisy systems

The projector formalism of Zwanzig-Mori type is extended to obtain generalized Fokker-Planck and generalized nonlinear Langevin equations for coarse-grained variables when the underlying microscopic dynamics is dissipative and noisy (stochastic).     

Simple generalization of Kramers theory to finite barrier height in spatial diffusion regime

Motivated by the escape process at low reduced barrier heights (measured in units of $k_{B}T$) is still a stationary one, the Kramers theoretical method in spatial diffusion regime should be applicable to this process. The Kramers theory is generalized to finite barrier height in a simple manner. The integration constant is redetermined by introducing metastable equilibrium state concept and continuous condition of the probability at the joint point of the potential barrier and potential well. The parabolic barrier with local frequency is replaced by a parabolic barrier with nonlocal frequency. The modified Kramers theory is confirmed by a cubic potential case. The maximal relative error in the spatial diffusion regime is less than 3% for the applied parameters.     

Chemical reaction rates and solvent friction

The role of the dynamic solvent friction in influencing the rates of chemical reactions in solution is described. Features considered include (a) the bias of the reaction coordinate toward a direction of lesser friction in the diffusive limit, (b) the importance of frequency-dependent friction in atom transfers, tunneling reactions and isomerizations, (c) the dynamic nonequilibrium solvation in charge transfers which leads to a polar solvent molecule reorientation time dependence for the rate, and (d)the importance of internal degrees of freedom in the location of the Kramers turnover for isomerizations.     

Uniform expansion of the transition rate in Kramers' problem

Kramers' model of diffusion over potential barriers, e.g., chemical reactions, based on the noise activated escape of a particle from a potential well, is considered. Kramers derived escape rates valid for intermediate and large damping, and in a separate analysis, for small damping. In the small damping limit, Kramers' intermediate result reduces to the transition state rate which does not agree with the small damping result. A new escape rate is derived that is uniformly valid for all values of the damping coefficient. The new rate reduces to Kramers' results in the appropriate limits and, in particular, connects Kramers' intermediate and small damping results.This work was partially supported by the Air Force Office of Scientific Research under Grant No. AFOSR-83-0086, U.S. Department of Energy under Grant No. DE-AC02-78ERO-4650, and the National Science Foundation under Grant No. MCS-83-00562. One of us (BJM) gratefully acknowledges the support of a John Simon Guggenheim Memorial Foundation Fellowship.     

Overview of theoretical models for reaction rates

There is enormous recent interest in the development of models for rate processes because rates are an almost universal characterization in the physical and biological sciences. In this paper we provide an introduction to several of the problems to be discussed in greater depth by other speakers at a symposium held at the National Institutes of Health on May 6–8, 1985. This review will focus on (1) the Smoluchowski model for reaction rates together with its extension by Onsager, (2) first passage time formalism for discrete and continuous master equations and Fokker-Planck equations, (3) the Kramers model and its extensions, (4) diffusion in the presence of trapping centers.     

Molecular dynamics study of reaction kinetics in viscous media

Predicted by stochastic models and observed experimentally in a number of isomerization reactions, viscosity-induced solvent effects manifest themselves in a significant departure of the reaction rates from the values expected on the basis of transition state theory. These effects are well understood within the framework of stochastic models; however, the predictive power of such models is limited by the fact that their parameters are not readily available. Experiment and molecular dynamics (MD) simulations can provide such information and can serve as the testing grounds for various stochastic models. In real solvents, a change in viscosity is inevitably associated with variation of at least one of the three factors – temperature, pressure, or solvent identity, resulting in different solvent–solvent and solvent–solute interactions. A model is proposed in which solvent viscosity is manipulated through mass scaling, which allows one to maintain other factors constant for a series of viscosities. This approach was tested on MD simulations of the kinetics of two model isomerization reactions in Lennard–Jones solvents, whose viscosity was varied over three orders of magnitude. The results reproduce the Kramers turnover and a strong negative viscosity dependence of the reaction rates in the high viscosity limit, somewhat weaker than η ^?1.     

Modified Kramers formulas for the decay rate in agreement with dynamical modeling

Accuracy of the Kramers approximate formulas for the thermal decay rate of the metastable state is studied for the anharmonic shapes of the potential pocket and the barrier. This is done by the comparison with the quasistationary rate resulting from the dynamical modeling. Disagreement between the Kramers rate and the dynamical one is shown to reach 15% in the cases when much better agreement is expected. Corrections to the Kramers formulas accounting for the higher derivatives of the potential are obtained. The small parameters are the ratios of the thermal energy to the stiffnesses at the extremes of the potential. The distance between the potential barrier and the absorptive border is accounted for as well. This corrected Kramers rate is demonstrated to agree with the dynamical rate typically within 2%. Probably the most interesting result is that despite the corrections are derived in the case of the overdamped Brownian motion, the above 2% agreement holds even in the case of medium friction.     

Random-matrix model for dissipative two-level systems

Assuming a random-matrix model for the system-bath interaction and using a series expansion for the evolution operator, we studied the relaxation of a nondegenerate two-level system. For times larger than the duration of a collision and smaller than the Poincaré recurrence time, we calculate the survival probability of still finding the system, at timet, in the same state in which it was prepared att=0. For a fixed initial state of the bath, we obtain an exponential transition rate, but when we average over initial states we may get a mixture of decay constants that could distroy the exponential behavior of the transition rate.     

A variational principle for boundary value problems in kinetic theory

A variational principle which applies directly to the integrodifferential form of the linearized Boltzmann equation is introduced. Extremely general boundary conditions and collision terms are allowed. For a class of interesting problems, the value of the functional to be varied is shown to be closely related to quantities of great physical interest. The formalism is applied to the treatment of plane Couette flow for different forms of the collision term (BGK model, rigid spheres, Maxwell's molecules).Research sponsored by the Air Force Office of Scientific Research under contract F 61(052)-68-C-0020, through the European Office of Aerospace Research, OAR, United States Air Force.     

Generalized enskog theory for homogeneous systems

We propose a generalization of the Enskog equation for homogeneous dense systems including the complete three-particle dynamics. To this end the time derivative of the one-particle distribution is represented in the thermodynamic limit as the sum of three terms describing the effect of the initials-particle correlations, collisions withins-particle clusters, and coupling ofs-particle clusters to the surrounding gaseous medium, respectively. The analysis of casess=2 ands=3 is performed both for hard spheres and for a smooth, repulsive interaction. On assuming the equilibrium structure and spatial dependence of terms reflecting the effect of the medium, we obtain fors=2 the Enskog equation, and fors=3 a new equation, going beyond the Enskog theory. Apart from the Enskog collision term it contains additional contributions, and can be shown to reduce to the Choh-Uhlenbeck equation in the long-time, low-density limit.     

Boussinesq方程组的广义变分原理

半反推法是何吉欢为了寻求物理问题的变分原理而提出的,可避免由拉氏乘子法引起的临界变分现象. 应用半反推法分别获得了描述水波运动的两类Boussinesq方程组的一族广义变分原理,并验证了它们的正确性. 关键词： 半反推法 广义变分原理 Boussinesq方程组     

Kramers time in weakly nonpotential systems

We consider a bistable Fokker-Planck system with a known stationary distribution and a small nonpotential part in the drift force. We perform a perturbation calculation of its Kramers time, _K, and compare it with the corresponding time, _K ⁽⁰⁾ , for the potential system which has the same stationary distribution. We show that _K/ _K ⁽⁰⁾ depends only on the properties of the drift force close to the saddle-point.The authors would like to dedicate this work to their colleagues Y. Orlov, R. Nazarian, and V. Brailovski.     

Microcanonical density functionals for critical systems: An exact one-dimensional example

Free-energy functionals suitable for describing realistic, nonuniform systems near criticality are discussed with emphasis on the advantages of a local formalism. It is proposed to investigatemicro canonical functionals in which both the usual order-parameter (or magnetization) density m(r)and the local energy density (r), which has independent critical fluctuations, are employed. This approach is tested by an exact calculation of the microcanonical functional [{m}, {}] in the continuum limit for a one-dimensional Ising model. Remarkably, the microcanonical functional is found to be local irrespective of the proximity to the critical point (located at zero temperature and zero field). Furthermore, its form relates closely to the scaling postulate advanced earlier by de Gennes and Fisher and displays features of conformal covariance.     

Progress and bottlenecks in simulating lattice gauge theory with fermions

We present a progress report in lattice gauge theory computer simulations which includes the effects of light, dynamical fermions. Microcanonical and hybrid microcanonical-Langevin alogrithms are presented and discussed. A method for “accelerating” stochastic differential equations and defeating critical slowing down is reviewed. Physics applications such as the thermodynamics of quantum chromodynamics, hierarchal energy scales in unified gauge theories, and the phase diagram of theories with many fermion species are discussed. Prospects for future research are assessed.     

Two-body exceptional points in open dissipative systems

We study two-body non-Hermitian physics in the context of an open dissipative system depicted by the Lindblad master equation.Adopting a minimal lattice model of a handful of interacting fermions with single-particle dissipation,we show that the non-Hermitian effective Hamiltonian of the master equation gives rise to two-body scattering states with state-and interaction-dependent parity-time transition.The resulting two-body exceptional points can be extracted from the trace-preserving density-matrix dynamics of the same dissipative system with three atoms.Our results not only demonstrate the interplay of parity-time symmetry and interaction on the exact few-body level,but also serve as a minimal illustration on how key features of non-Hermitian few-body physics can be probed in an open dissipative many-body system.