Spatio-temporal

Radiation probes such as neutrons, x-rays and visible light are used to see the structure of physical systems tlirough elastic scattering experunents. Inelastic scattering experiments measure both the structural and dynamical correlations that exist in a physical system. For a system which is in thennodynamic equilibrium, the molecular dynamics create spatio-temporal correlations which are the manifestation of themial fluctuations around the equilibrium state. For a condensed phase system, dynamical correlations are intimately linked to its structure. For systems in equilibrium, linear response tiieory is an appropriate framework to use to inquire on the spatio-temporal correlations resulting from thennodynamic fluctuations. Appropriate response and correlation functions emerge naturally in this framework, and the role of theory is to understand these correlation fiinctions from first principles. This is the subject of section A3.3.2. 

A system of interest may be macroscopically homogeneous or inliomogeneous. The inliomogeneity may arise on account of interfaces between coexisting phases in a system or due to the system s finite size and proximity to its external surface. Near the surfaces and interfaces, the system s translational synnnetry is broken this has important consequences. The spatial structure of an inliomogeneous system is its average equilibrium property and has to be incorporated in the overall theoretical stnicture, in order to study spatio-temporal correlations due to themial fluctuations around an inliomogeneous spatial profile. This is also illustrated in section A3.3.2. 

Another possibility is that a system may be held in a constrained equilibrium by external forces and thus be in a non-equilibrium steady state (NESS). In this case, the spatio-temporal correlations contain new ingredients, which are also exemplified in section A3.3.2. 

A3.3.2 EQUILIBRIUM SYSTEMS THERMAL FLUCTUATIONS AND SPATIO-TEMPORAL CORRELATIONS... 

We shall describe some of tire common types of chemical patterns observed in such experiments and comment on tire mechanisms for tlieir appearance. In keeping witli tire tlieme of tliis chapter we focus on states of spatio-temporal chaos or on regular chemical patterns tliat lead to such turbulent states. We shall touch only upon tire main aspects of tliis topic since tliere is a large variety of chemical patterns and many mechanisms for tlieir onset [2,3, 5,31]. 

The cores of the spiral waves need not be stationary and can move in periodic, quasi-periodic or even chaotic flower trajectories [42, 43]. In addition, spatio-temporal chaos can arise if such spiral waves break up and the spiral wave fragments spawn pairs of new spirals [42, 44]. 

Figure C3.6.11 Defect-mediated turbulence in tire BZ reaction, (a) Spatial stmcture close to tire instability, (b) Fully developed spatio-temporal turbulence. The control parameter is tire concentration of H2SO4 in tire feed reactor. Reproduced by pennission from Ouyang and Flesselles [501.

The local dynamics of tire systems considered tluis far has been eitlier steady or oscillatory. However, we may consider reaction-diffusion media where tire local reaction rates give rise to chaotic temporal behaviour of tire sort discussed earlier. Diffusional coupling of such local chaotic elements can lead to new types of spatio-temporal periodic and chaotic states. It is possible to find phase-synchronized states in such systems where tire amplitude varies chaotically from site to site in tire medium whilst a suitably defined phase is synclironized tliroughout tire medium 51. Such phase synclironization may play a role in layered neural networks and perceptive processes in mammals. Somewhat suriDrisingly, even when tire local dynamics is chaotic, tire system may support spiral waves... 

If tlie diffusion coefficients of tlie chemical species are sufficiently different, new types of chemical instability arise which can lead to tlie fonnation of chemical patterns and ultimately to spatio-temporal chaotic behaviour. 

One may also observe a transition to a type of defect-mediated turbulence in this Turing system (see figure C3.6.12 (b). Here the defects divide the system into domains of spots and stripes. The defects move erratically and lead to a turbulent state characterized by exponential decay of correlations [59]. Turing bifurcations can interact with the Hopf bifurcations discussed above to give rise to very complicated spatio-temporal patterns [63, 64]. 

Figure C3.6.14 Space-time (y,t) plot of the minima (black) in the cubic autocatalysis front ( )(y,t) in equation C3.6.16 showing the nature of the spatio-temporal chaos.

Several methods have been employed to study chemical reactions theoretically. Mean-field modeling using ordinary differential equations (ODE) is a widely used method [8]. Further extensions of the ODE framework to include diffusional terms are very useful and, e.g., have allowed one to describe spatio-temporal patterns in diffusion-reaction systems [9]. However, these methods are essentially limited because they always consider average environments of reactants and adsorption sites, ignoring stochastic fluctuations and correlations that naturally emerge in actual systems e.g., very recently by means of in situ STM measurements it has been demon-... 

The HS model exhibits a rich variety of spatio-temporal patterns. During the oscillatory behavior, if the simulation starts with an empty grid in the hexagonal phase the only possible event is CO adsorption. Consequently, when a certain CO coverage is reached, the surface starts to convert into the 1 X 1 phase. Oxygen cannot adsorb yet, due to the lack of empty sites. 

D. Walgraef. Spatio-Temporal Pattern Formation. New York Springer Verlag, 1997, pp. 1-301. 

M. Tammaro, M. Sabella, J. W. Evans. Hybrid treatment of spatio-temporal behavior in surface reactions with coexisting immobile and highly mobile reactants. J Chem Phys 705 10277-10285, 1995. 

R. J. Gelten et al. Monte Carlo simulation of a surface reaction model showing spatio-temporal pattern formations and oscillations. J Chem Phys 705 5921-5934, 1998. 

S. Jabubith, H. H. Rotermund, W. Engel, A. von Oertzen, G. Ertl. Spatio-temporal concentration patterns in a surface reaction Propagation of standing waves, rotating spirals and turbulence. Phys Rev Lett 65 3013-3016, 1990. 

Dimensions The limits of the set and measure entropies as T, B —> oo yield the spatio-temporal set and measure dimensions, respectively ... 

Dynamical Entropy In order to capture the dynamics of a CML pattern, Kaneko has constructed what amounts to it mutual information between two successive patterns at a given time interval [kaneko93]. It is defined by first obtaining an estimate, through spatio-temporal samplings, of the probability transition matrix Td,d = transition horn domain of size D to a domain of size D. The dynamical entropy, Sd, is then given by... 

We recall from our earlier discussion of chaos in one-dimensional continuous systems (see section 4.1) that period-doubling is not the only mechanism by which chaos can be generated. Another frequently occurring route to chaos is intermittency. But while intermittency in low dimensional dynamical systems appears to be constrained to purely temporal behavior [pomeau80], CMLs exhibit a spatio-temporal intermittency in which laminar eddies are intermixed with turbulent regions in a complex pattern in space-time. 

K. Asakura, J. Lanterbach, H.H. Rothermund, and G. Ertl, Spatio-temporal pattern formation during catalytic CO oxidation on a Pt(100) surface modified with submonolayers of Au, Surf. Sci. 374, 125-141 (1997). 

What Is Interferometry (1.3) Interferometry deals with the physical phenomena which result from the superposition of electromagnetic (e.m.) waves. Practically, interferometry is used throughout the electromagnetic spectrum astronomers use predominantly the spectral regime from radio to the near UV. Essential to interferometry is that the radiation emerges from a single source and travels along different paths to the point where it is detected. The spatio-temporal coherence characteristics of the radiation is studied with the interferometer to obtain information about the physical nature of the source. 

Figure 2.16. Computer simulation of spatio-temporal pattern formation in CO oxidation on a surface. [Adapted from R.J. Celten, A.P.J. Jansen, R.A. van Santen, j.j. Lukkien, j.P.L Segers and P.A.j. Hilbers,j. Chem. Phys. 108 (1998) 5921.]...

The spatio-temporal variations of the concentration field in turbulent mixing processes are associated wdth very different conditions for chemical reactions in different parts of a reactor. This scenario usually has a detrimental effect on the selectivity of reactions when the reaction time-scale is small compared with the mixing time-scale. Under the same conditions (slow mixing), the process times are increased considerably. Due to mass transfer inhibitions, the true kinetics of a reaction does not show up instead, the mixing determines the time-scale of a process. This effect is known as mixing masking of reactions [126]. 

A multitude of information is supplied on the spatio-temporal temperature evolution at the outside of the reactor housing and via conduits even within the micro reactor (bottom) [15]. 

For the catalytic oxidation of malonic acid by bromate (the Belousov-Zhabotinskii reaction), fimdamental studies on the interplay of flow and reaction were made. By means of capillary-flow investigations, spatio-temporal concentration patterns were monitored which stem from the interaction of a specific complex reaction and transport of reaction species by molecular diffusion [68]. One prominent class of these patterns is propagating reaction fronts. By external electrical stimulus, electromigration of ionic species can be investigated. 

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