About Bifurcational Parametric Simplification

TL;DR

This paper introduces the concept of bifurcational parametric simplification, explaining how bifurcations in chemical systems can simplify mechanisms and aid in parameter identification, with applications demonstrated on the Langmuir mechanism.

Contribution

It generalizes the idea of critical simplification to bifurcational parametric simplification and applies invariant manifold methods to analyze bifurcations in chemical kinetics.

Findings

Bifurcations correspond to parameter dependencies and simplifications.

Maximal bifurcation complexity minimizes independent parameters.

Method enables parameter identification from single experiments.

Abstract

A concept of "critical" simplification was proposed by Yablonsky and Lazman in 1996 for the oxidation of carbon monoxide over a platinum catalyst using a Langmuir-Hinshelwood mechanism. The main observation was a simplification of the mechanism at ignition and extinction points. The critical simplification is an example of a much more general phenomenon that we call \emph{a bifurcational parametric simplification}. Ignition and extinction points are points of equilibrium multiplicity bifurcations, i.e., they are points of a corresponding bifurcation set for parameters. Any bifurcation produces a dependence between system parameters. This is a mathematical explanation and/or justification of the "parametric simplification". It leads us to a conjecture that "maximal bifurcational parametric simplification" corresponds to the "maximal bifurcation complexity." This conjecture can have practical applications for experimental study, because at points of "maximal bifurcation complexity" the number of independent system parameters is minimal and all other parameters can be evaluated analytically or numerically. We illustrate this method by the case of the simplest possible bifurcation, that is a multiplicity bifurcation of equilibrium and we apply this analysis to the Langmuir mechanism. Our analytical study is based on a coordinate-free version of the method of invariant manifolds (proposed recently in 2006 ). As a result we obtain a more accurate description of the "critical (parametric) simplifications." With the help of the "bifurcational parametric simplification" kinetic mechanisms and reaction rate parameters may be readily identified from a monoparametric experiment (reaction rate vs. reaction parameter).