Kryvohuz Maksym, Mukamel Shaul
Chemical Sciences and Engineering Division, Argonne National Laboratory, Argonne, Illinois 60439, USA.
Chemistry Department, University of California, Irvine, California 92697-2025, USA.
J Chem Phys. 2014 Jan 21;140(3):034111. doi: 10.1063/1.4861588.
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.
本文提出了一种化学动力学非线性响应理论，该理论利用多重微扰来探究非线性化学系统的时间演化。推导了可作为动力学路径和速率的多维度量的非线性化学反应函数和磁化率的表达式。还引入了一类结合多重微扰和测量的新型多维度量。提出了稳态化学系统的非线性涨落耗散关系，该关系取代了浓度测量和微扰操作。提供了几个用于复杂反应机理分析的应用实例。
