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Nonlinear response theory in chemical kinetics
Maksym Kryvohuz1, Shaul Mukamel2
1Chemical Sciences and Engineering Division, Argonne National Laboratory, Argonne, Illinois 60439, USA.
Abstract:
A theory of nonlinear response of chemical kinetics, in which multiple perturbations are used to probe the time evolution of nonlinear chemical systems, is developed. Expressions for nonlinear chemical response functions and susceptibilities, which can serve as multidimensional measures of the kinetic pathways and rates, are derived. A new class of multidimensional measures that combine multiple perturbations and measurements is also introduced. Nonlinear fluctuation-dissipation relations for steady-state chemical systems, which replace operations of concentration measurement and perturbations, are proposed. Several applications to the analysis of complex reaction mechanisms are provided.
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