Front propagation techniques to calculate the largest Lyapunov exponent of dilute hard disk gases

A kinetic approach is adopted to describe the exponential growth of a small deviation of the initial phase space point, measured by the largest Lyapunov exponent, for a dilute system of hard disks, both in equilibrium and in a uniform shear flow. We derive a generalized Boltzmann equation for an extended one-particle distribution that includes deviations from the reference phase space point. The equation is valid for very low densities n, and requires an unusual expansion in powers of 1/|ln n|. It reproduces and extends results from the earlier, more heuristic clock model and may be interpreted as describing a front propagating into an unstable state. The asymptotic speed of propagation of the front is proportional to the largest Lyapunov exponent of the system. Its value may be found by applying the standard front speed selection mechanism for pulled fronts to the case at hand. For the equilibrium case, an explicit expression for the largest Lyapunov exponent is given and for sheared systems we give explicit expressions that may be evaluated numerically to obtain the shear rate dependence of the largest Lyapunov exponent.Comment: 26 pages REVTeX, 1 eps figure. Added remarks, a reference and corrected some typo

Kinetic Theory Estimates for the Kolmogorov-Sinai Entropy and the Largest Lyapunov Exponents for Dilute, Hard-Ball Gases and for Dilute, Random Lorentz Gases

The kinetic theory of gases provides methods for calculating Lyapunov exponents and other quantities, such as Kolmogorov-Sinai entropies, that characterize the chaotic behavior of hard-ball gases. Here we illustrate the use of these methods for calculating the Kolmogorov-Sinai entropy, and the largest positive Lyapunov exponent, for dilute hard-ball gases in equilibrium. The calculation of the largest Lyapunov exponent makes interesting connections with the theory of propagation of hydrodynamic fronts. Calculations are also presented for the Lyapunov spectrum of dilute, random Lorentz gases in two and three dimensions, which are considerably simpler than the corresponding calculations for hard-ball gases. The article concludes with a brief discussion of some interesting open problems.Comment: 41 pages (REVTEX); 7 figs., 4 of which are included in LaTeX source. (Fig.7 doesn't print well on some printers) This revised paper will appear in "Hard Ball Systems and the Lorentz Gas", D. Szasz ed., Encyclopaedia of Mathematical Sciences, Springe

Controlling Molecular Scattering by Laser-Induced Field-Free Alignment

We consider deflection of polarizable molecules by inhomogeneous optical fields, and analyze the role of molecular orientation and rotation in the scattering process. It is shown that molecular rotation induces spectacular rainbow-like features in the distribution of the scattering angle. Moreover, by preshaping molecular angular distribution with the help of short and strong femtosecond laser pulses, one may efficiently control the scattering process, manipulate the average deflection angle and its distribution, and reduce substantially the angular dispersion of the deflected molecules. We provide quantum and classical treatment of the deflection process. The effects of strong deflecting field on the scattering of rotating molecules are considered by the means of the adiabatic invariants formalism. This new control scheme opens new ways for many applications involving molecular focusing, guiding and trapping by optical and static fields

Constructing smooth potentials of mean force, radial, distribution functions and probability densities from sampled data

In this paper a method of obtaining smooth analytical estimates of probability densities, radial distribution functions and potentials of mean force from sampled data in a statistically controlled fashion is presented. The approach is general and can be applied to any density of a single random variable. The method outlined here avoids the use of histograms, which require the specification of a physical parameter (bin size) and tend to give noisy results. The technique is an extension of the Berg-Harris method [B.A. Berg and R.C. Harris, Comp. Phys. Comm. 179, 443 (2008)], which is typically inaccurate for radial distribution functions and potentials of mean force due to a non-uniform Jacobian factor. In addition, the standard method often requires a large number of Fourier modes to represent radial distribution functions, which tends to lead to oscillatory fits. It is shown that the issues of poor sampling due to a Jacobian factor can be resolved using a biased resampling scheme, while the requirement of a large number of Fourier modes is mitigated through an automated piecewise construction approach. The method is demonstrated by analyzing the radial distribution functions in an energy-discretized water model. In addition, the fitting procedure is illustrated on three more applications for which the original Berg-Harris method is not suitable, namely, a random variable with a discontinuous probability density, a density with long tails, and the distribution of the first arrival times of a diffusing particle to a sphere, which has both long tails and short-time structure. In all cases, the resampled, piecewise analytical fit outperforms the histogram and the original Berg-Harris method.Comment: 14 pages, 15 figures. To appear in J. Chem. Phy

An Extension of the Fluctuation Theorem

Heat fluctuations are studied in a dissipative system with both mechanical and stochastic components for a simple model: a Brownian particle dragged through water by a moving potential. An extended stationary state fluctuation theorem is derived. For infinite time, this reduces to the conventional fluctuation theorem only for small fluctuations; for large fluctuations, it gives a much larger ratio of the probabilities of the particle to absorb rather than supply heat. This persists for finite times and should be observable in experiments similar to a recent one of Wang et al.Comment: 12 pages, 1 eps figure in color (though intelligible in black and white

Electric Deflection of Rotating Molecules

We provide a theory of the deflection of polar and non-polar rotating molecules by inhomogeneous static electric field. Rainbow-like features in the angular distribution of the scattered molecules are analyzed in detail. Furthermore, we demonstrate that one may efficiently control the deflection process with the help of short and strong femtosecond laser pulses. In particular the deflection process may by turned-off by a proper excitation, and the angular dispersion of the deflected molecules can be substantially reduced. We study the problem both classically and quantum mechanically, taking into account the effects of strong deflecting field on the molecular rotations. In both treatments we arrive at the same conclusions. The suggested control scheme paves the way for many applications involving molecular focusing, guiding, and trapping by inhomogeneous fields

Effective pair potentials for spherical nanoparticles

An effective description for spherical nanoparticles in a fluid of point particles is presented. The points inside the nanoparticles and the point particles are assumed to interact via spherically symmetric additive pair potentials, while the distribution of points inside the nanoparticles is taken to be spherically symmetric and smooth. The resulting effective pair interactions between a nanoparticle and a point particle, as well as between two nanoparticles, are then given by spherically symmetric potentials. If overlap between particles is allowed, the effective potential generally has non-analytic points, but for each effective potential the expressions for different overlapping cases can be written in terms of one analytic auxiliary potential. Effective potentials for hollow nanoparticles (appropriate e.g. for buckyballs) are also considered, and shown to be related to those for solid nanoparticles. Finally, explicit expressions are given for the effective potentials derived from basic pair potentials of power law and exponential form, as well as from the commonly used London-Van der Waals, Morse, Buckingham, and Lennard-Jones potential. The applicability of the latter is demonstrated by comparison with an atomic description of nanoparticles with an internal face centered cubic structure.Comment: 27 pages, 12 figures. Unified description of overlapping and nonoverlapping particles added, as well as a comparison with an idealized atomic descriptio