Matyushov Dmitry V
Center for Biological Physics, Arizona State University, P.O. Box 871504, Tempe, Arizona 85287-1504, USA.
J Chem Phys. 2009 Apr 28;130(16):164522. doi: 10.1063/1.3119639.
A theoretical formulation is developed for the activated kinetics when some subset of nuclear modes of the thermal bath is slower than the reaction and ergodicity of the thermal bath is not maintained. Nonergodic free energy profiles along the reaction coordinate are constructed by using restricted canonical ensembles with the phase space available to the system found by solving a self-consistent kinetic equation. The resulting activation barrier incorporates not only thermodynamic parameters but also dynamical information from the time autocorrelation function of the solute-solvent interaction energy. The theory is applied to the reactions of solvolysis and charge transfer in polar media.
当热浴的某些核模式子集比反应慢且热浴的遍历性不保持时，发展了一种用于活化动力学的理论公式。通过使用受限正则系综，沿着反应坐标构建非遍历自由能分布，其中系统可用的相空间通过求解自洽动力学方程来确定。由此产生的活化能垒不仅包含热力学参数，还包含来自溶质 - 溶剂相互作用能的时间自相关函数的动力学信息。该理论应用于极性介质中的溶剂解反应和电荷转移反应。
