4.7 Article

Nonlinear response theory in chemical kinetics

Journal

JOURNAL OF CHEMICAL PHYSICS
Volume 140, Issue 3, Pages -

Publisher

AMER INST PHYSICS
DOI: 10.1063/1.4861588

Keywords

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Funding

  1. National Science Foundation (NSF) [CHE-1058791]
  2. Chemical Sciences, Geosciences, and Biosciences Division, Office of Basic Energy Sciences, Office of Science, U.S. Department of Energy (DOE)
  3. NIH [GM-59230]
  4. Direct For Mathematical & Physical Scien [1361516] Funding Source: National Science Foundation
  5. Division Of Chemistry [1361516] Funding Source: National Science Foundation

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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. (C) 2014 AIP Publishing LLC.

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