Mesoscopic Multi-Particle Collision Dynamics of Reaction-Diffusion Fronts

A mesoscopic multi-particle collision model for fluid dynamics is generalized to incorporate the chemical reactions among species that may diffuse at different rates. This generalization provides a means to simulate reaction-diffusion dynamics of complex reactive systems. The method is illustrated by a study of cubic autocatalytic fronts. The mesoscopic scheme is able to reproduce the results of reaction-diffusion descriptions under conditions where the mean field equations are valid. The model is also able to incorporate the effects of molecular fluctuations on the reactive dynamics.Comment: 5 pages, 4 figure

Mesoscopic Model for Diffusion-Influenced Reaction Dynamics

A hybrid mesoscopic multi-particle collision model is used to study diffusion-influenced reaction kinetics. The mesoscopic particle dynamics conserves mass, momentum and energy so that hydrodynamic effects are fully taken into account. Reactive and non-reactive interactions with catalytic solute particles are described by full molecular dynamics. Results are presented for large-scale, three-dimensional simulations to study the influence of diffusion on the rate constants of the A+CB+C reaction. In the limit of a dilute solution of catalytic C particles, the simulation results are compared with diffusion equation approaches for both the irreversible and reversible reaction cases. Simulation results for systems where the volume fraction of catalytic spheres is high are also presented, and collective interactions among reactions on catalytic spheres that introduce volume fraction dependence in the rate constants are studied.Comment: 9 pages, 5 figure

Resonantly Forced Inhomogeneous Reaction-Diffusion Systems

The dynamics of spatiotemporal patterns in oscillatory reaction-diffusion systems subject to periodic forcing with a spatially random forcing amplitude field are investigated. Quenched disorder is studied using the resonantly forced complex Ginzburg-Landau equation in the 3:1 resonance regime. Front roughening and spontaneous nucleation of target patterns are observed and characterized. Time dependent spatially varying forcing fields are studied in the 3:1 forced FitzHugh-Nagumo system. The periodic variation of the spatially random forcing amplitude breaks the symmetry among the three quasi-homogeneous states of the system, making the three types of fronts separating phases inequivalent. The resulting inequality in the front velocities leads to the formation of ``compound fronts'' with velocities lying between those of the individual component fronts, and ``pulses'' which are analogous structures arising from the combination of three fronts. Spiral wave dynamics is studied in systems with compound fronts.Comment: 14 pages, 19 figures, to be published in CHAOS. This replacement has some minor changes in layout for purposes of neatnes

Quantum-Classical Wigner-Liouville Equation

We consider a quantum system that is partitioned into a subsystem and a bath. Starting from the Wigner transform of the von Neumann equation for the quantum-mechanical density matrix of the entire system, the quantum-classical Wigner-Liouville equation is obtained in the limit where the masses M of the bath particles are large as compared with the masses m of the subsystem particles. The structure of this equation is discussed and it is shown how the abstract operator form of the quantum-classical Liouville equation is obtained by taking the inverse Wigner transform on the subsystem. Solutions in terms of classical trajectory segments and quantum transition or momentum jumps are described.Розглянуто квантову систему, розділену на підсистему та термостат. Після застосування перетворень Вігнера до рівняння фон Неймана для квантово-механічної матриці щільності системи одержано квантово-класичне рівняння Вігнера-Ліувілля у границі, де маси M частинок термостату великі у порівнянні з масами m частинок підсистеми. Обговорено структуру цього рівняння і показано, як можна отримати абстрактну операторну форму квантово-класичного рівняння Ліувілля за допомогою зворотного перетворення Вігнера на підсистемі. Розв'язки описано в термінах класичних сегментів траєкторії та квантового переходу або імпульсних стрибків

Renormalized Equilibria of a Schloegl Model Lattice Gas

A lattice gas model for Schloegl's second chemical reaction is described and analyzed. Because the lattice gas does not obey a semi-detailed-balance condition, the equilibria are non-Gibbsian. In spite of this, a self-consistent set of equations for the exact homogeneous equilibria are described, using a generalized cluster-expansion scheme. These equations are solved in the two-particle BBGKY approximation, and the results are compared to numerical experiment. It is found that this approximation describes the equilibria far more accurately than the Boltzmann approximation. It is also found, however, that spurious solutions to the equilibrium equations appear which can only be removed by including effects due to three-particle correlations.Comment: 21 pages, REVTe

Spatio-temporal dynamics induced by competing instabilities in two asymmetrically coupled nonlinear evolution equations

Pattern formation often occurs in spatially extended physical, biological and chemical systems due to an instability of the homogeneous steady state. The type of the instability usually prescribes the resulting spatio-temporal patterns and their characteristic length scales. However, patterns resulting from the simultaneous occurrence of instabilities cannot be expected to be simple superposition of the patterns associated with the considered instabilities. To address this issue we design two simple models composed by two asymmetrically coupled equations of non-conserved (Swift-Hohenberg equations) or conserved (Cahn-Hilliard equations) order parameters with different characteristic wave lengths. The patterns arising in these systems range from coexisting static patterns of different wavelengths to traveling waves. A linear stability analysis allows to derive a two parameter phase diagram for the studied models, in particular revealing for the Swift-Hohenberg equations a co-dimension two bifurcation point of Turing and wave instability and a region of coexistence of stationary and traveling patterns. The nonlinear dynamics of the coupled evolution equations is investigated by performing accurate numerical simulations. These reveal more complex patterns, ranging from traveling waves with embedded Turing patterns domains to spatio-temporal chaos, and a wide hysteretic region, where waves or Turing patterns coexist. For the coupled Cahn-Hilliard equations the presence of an weak coupling is sufficient to arrest the coarsening process and to lead to the emergence of purely periodic patterns. The final states are characterized by domains with a characteristic length, which diverges logarithmically with the coupling amplitude.Comment: 9 pages, 10 figures, submitted to Chao

Front explosion in a periodically forced surface reaction

Resonantly forced oscillatory reaction-diffusion systems can exhibit fronts with complicated interfacial structure separating phase-locked homogeneous states. For values of the forcing amplitude below a critical value the front "explodes" and the width of the interfacial zone grows without bound. Such front explosion phenomena are investigated for a realistic model of catalytic CO oxidation on a Pt(110) surface in the 2:1 and 3:1 resonantly forced regimes. In the 2:1 regime, the fronts are stationary and the front explosion leads to a defect-mediated turbulent state. In the 3:1 resonantly forced system, the fronts propagate. The front velocity tends to zero as the front explosion point is reached and the final asymptotic state is a 2:1 resonantly locked labyrinthine pattern. The front dynamics described here should be observable in experiment since the model has been shown to capture essential features of the CO oxidation reaction

Spot deformation and replication in the two-dimensional Belousov-Zhabotinski reaction in water-in-oil microemulsion

In the limit of large diffusivity ratio, spot-like solutions in the two-dimensional Belousov-Zhabotinski reaction in water-in-oil microemulsion are studied. It is shown analytically that such spots undergo an instability as the diffusivity ratio is decreased. An instability threshold is derived. For spots of small radius, it is shown that this instability leads to a spot splitting into precisely two spots. For larger spots, it leads to deformation, fingering patterns and space-filling curves. Numerical simulations are shown to be in close agreement with the analytical predictions.Comment: To appear, PR

Role of an intermediate state in homogeneous nucleation

We explore the role of an intermediate state (phase) in homogeneous nucleation phenomenon by examining the decay process through a doubly-humped potential barrier. As a generic model we use the fourth- and sixth-order Landau potentials and analyze the Fokker-Planck equation for the one-dimensional thermal diffusion in the system characterized by a triple-well potential. In the low temperature case we apply the WKB method to the decay process and obtain the decay rate which is accurate for a wide range of depth and curvature of the middle well. In the case of a deep middle well, it reduces to a doubly-humped-barrier counterpart of the Kramers escape rate: the barrier height and the curvature of an initial well in the Kramers rate are replaced by the arithmetic mean of higher(or outer) and lower(or inner) partial barriers and the geometric mean of curvatures of the initial and intermediate wells, respectively. It seems to be a universal formula. In the case of a shallow-enough middle well, Kramers escape rate is alternatively evaluated within the standard framework of the mean-first-passage time problem, which certainly supports the WKB result. The criteria whether or not the existence of an intermediate state can enhance the decay rate are revealed.Comment: 9pages, 11figure