Dynamic and static limitation in multiscale reaction networks, revisited

Details Dynamic and static limitation in multiscale reaction networks, revisited Dynamic and static limitation in multiscale reaction networks, revisited

2007-03-30

arxiv.org/abs/physics/0703278v4

Advances in Chemical Engineering, Volume 34 (2008), 103-173

Physics

Chemical Physics

Extended version with new examples. Accepted for publication in Adv. Chem. Eng

Scientific paper

10.1016/S0065-2377(08)00003-3

The concept of limiting step gives the limit simplification: the whole network behaves as a single step. However, in its simplest form this idea is applicable only to the simplest linear cycles in steady states. For such the simplest cycles the nonstationary behaviour is also limited by a single step, but not the same step that limits the stationary rate. We develop a general theory of static and dynamic limitation for all linear multiscale networks. New estimates of eigenvectors for diagonally dominant matrices are used. Multiscale ensembles of reaction networks with well separated constants are introduced and typical properties of such systems are studied. For any given ordering of reaction rate constants the explicit approximation of steady state, relaxation spectrum and related eigenvectors ("modes") is presented. The obtained multiscale approximations that we call "dominant systems" are computationally cheap and robust. These dominant systems can be used for direct computation of steady states and relaxation dynamics, especially when kinetic information is incomplete, for design of experiments and mining of experimental data, and could serve as a robust first approximation in perturbation theory or for preconditioning.

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