Kolb Jakob J, Angioletti-Uberti Stefano, Dzubiella Joachim
Institut für Physik, Humboldt-Universität zu Berlin, 12489 Berlin, Germany.
International Center for Soft Matter Research, Beijing University of Chemical Technology, Beijing 100029, China.
J Chem Phys. 2016 Feb 28;144(8):081102. doi: 10.1063/1.4942998.
We investigate the influence of a stochastically fluctuating step-barrier potential on bimolecular reaction rates by exact analytical theory and stochastic simulations. We demonstrate that the system exhibits a new "resonant reaction" behavior with rate enhancement if an appropriately defined fluctuation decay length is of the order of the system size. Importantly, we find that in the proximity of resonance, the standard reciprocal additivity law for diffusion and surface reaction rates is violated due to the dynamical coupling of multiple kinetic processes. Together, these findings may have important repercussions on the correct interpretation of various kinetic reaction problems in complex systems, as, e.g., in biomolecular association or catalysis.
我们通过精确的解析理论和随机模拟研究了随机波动的阶梯势垒对双分子反应速率的影响。我们证明,如果适当定义的波动衰减长度与系统大小相当,该系统会表现出一种新的“共振反应”行为,反应速率会增强。重要的是,我们发现,在共振附近,由于多个动力学过程的动态耦合,扩散和表面反应速率的标准倒数加和定律被违反。总之,这些发现可能会对复杂系统中各种动力学反应问题的正确解释产生重要影响,例如在生物分子缔合或催化过程中。