Chaki Nirmalya Kumar, Kakade Bhalchandra, Vijayamohanan Kunjukrishna Pillai, Singh Poonam, Dharmadhikari C V
Physical and Materials Chemistry Division, National Chemical Laboratory, Pune 411008, India.
Phys Chem Chem Phys. 2006 Apr 21;8(15):1837-44. doi: 10.1039/b516650k. Epub 2006 Mar 7.
In this article, the effect of interparticle interactions of 4.63 nm sized monolayer protected gold clusters (Au MPCs) during quantized double layer (QDL) charging has been investigated using electrochemical techniques. Voltammetry and scanning tunneling microscopy have been used to compare their electron transfer behavior. Furthermore, since the QDL process is diffusion controlled, the diffusion coefficient values have been estimated at various charge steps using two independent electroanalytical techniques, viz. chronoamperometry and impedance. These results show that higher core charge facilitates higher diffusion coefficient values, and indicate that repulsive interactions dominate for charged MPCs compared to those of its neutral analogue, which are mainly attractive in nature. Additionally, the electron transfer rate constants at various charge steps have been estimated from the impedance results, showing comparatively faster electron transfer rate at higher charge states.
在本文中，利用电化学技术研究了尺寸为4.63纳米的单层保护金团簇（Au MPCs）在量子化双层（QDL）充电过程中的粒子间相互作用的影响。伏安法和扫描隧道显微镜已被用于比较它们的电子转移行为。此外，由于QDL过程是扩散控制的，已使用两种独立的电分析技术，即时电流法和阻抗法，在不同的充电步骤估计扩散系数值。这些结果表明，更高的核心电荷促进了更高的扩散系数值，并表明与中性类似物相比，带电MPCs的排斥相互作用占主导地位，而中性类似物的相互作用主要是吸引性的。此外，已根据阻抗结果估计了不同充电步骤下的电子转移速率常数，结果表明在较高电荷状态下电子转移速率相对较快。
