Department of Chemistry, Saint Louis University, 3501 Laclede Ave., St. Louis, MO 63103, USA.
Phys Chem Chem Phys. 2011 Sep 14;13(34):15483-91. doi: 10.1039/c1cp21429b. Epub 2011 Aug 2.
Experiments are carried out in dual electrode oscillatory Ni electrodissolution in which the two electrodes have different surface areas. The transition to phase synchronization is analyzed as asymmetrical coupling strength, induced by placing a cross resistance between the electrodes, is varied. It is shown that because of nonisochronicity (phase shear, i.e., strong dependence of period on amplitude) of the oscillators, anomalous phase synchronization effects can be observed: advanced/delayed synchronization and, to a lesser extent, frequency difference enhancement. The type of synchronization is strongly affected by the underlying heterogeneities of the oscillators; in the experiments with a slow driver (large surface area) electrode the synchronization is advanced, with a fast driver electrode the synchronization is delayed with respect to symmetrical coupling. The findings thus reveal that the interplay of asymmetrical coupling with the types of inherent heterogeneities plays an important role for the interpretation of size effects in the dynamical behavior of a nonlinear chemical reaction.
在双电极振荡镍电解中进行实验，其中两个电极具有不同的表面积。通过在电极之间放置交叉电阻来改变非对称耦合强度，分析了向相位同步的转变。结果表明，由于振荡器的非等时性（相位剪切，即周期对振幅的强烈依赖性），可以观察到异常的相位同步效应：超前/延迟同步，以及在较小程度上，频率差增强。同步的类型受振荡器的固有异质性的强烈影响；在具有慢驱动（大表面积）电极的实验中，同步是超前的，而在具有快驱动电极的实验中，同步相对于对称耦合是延迟的。因此，这些发现揭示了非对称耦合与固有异质性类型的相互作用在解释非线性化学反应动力学行为中的大小效应方面起着重要作用。
