Chaos An Interdisciplinary Journal of Nonlinear Science · 2008 · 33 citations · 25 references
Natural SciencesChemistryDynamical SystemsElectrochemical EngineeringElectrochemistryBifurcation TheoryCoupled Cluster TheoryElectrochemical CellsElectrochemical ThermodynamicsElectrode-electrolyte InterfacesReaction DynamicsCluster PatternsElectrochemical Reaction MechanismsLimit Cycle DynamicsLimit Cycle OscillationsLocal OscillatorsMultistabilityRelaxation OscillationsRelaxation Oscillators
We studied the dynamics of a prototypical electrochemical model, the electro-oxidation of hydrogen in the presence of poisons, under galvanostatic conditions. The lumped system exhibits relaxation oscillations, which develop mixed-mode oscillations (MMOs) for low preset currents. A fast-slow analysis of the homogeneous dynamics reveals that the MMOs arise from a fast oscillating subsystem and a one-dimensional slow manifold. In the spatially extended system, the galvanostatic constraint imposes a synchronizing global coupling that drives the system into cluster patterns. The properties of the cluster patterns (CPs) result from an intricate interplay of the nature of the local oscillators, the global constraint, and a nonlocal coupling through the electrolyte. In particular, we find that the global constraint suppresses small-amplitude oscillations of MMOs and prevents domains oscillating out of phase from occupying equal regions in phase space. The nonlocal coupling causes each individual clustered region to oscillate on a different limit cycle. Typically multistability of CPs is found. Coexisting patterns possess different oscillation periods and a different total fraction in space that occupies the in-phase or out-of-phase state, respectively.
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Emerging Coherence in a Population of Chemical Oscillators
István Z. Kiss, Yumei Zhai, John L. Hudson · Science · 2002 · 502 citations