Das Ashok K, Hsiao Pai-Yi
Department of Engineering and System Science, National Tsing Hua University, Hsinchu, Taiwan.
J Chem Phys. 2015 Feb 28;142(8):084902. doi: 10.1063/1.4908563.
Langevin dynamics simulations are performed to study the response of charged dendrimers in alternating current electric fields in 3:1 salt solutions. Time evolutions of molecular size show breathing characteristics which take saw-tooth-like patterns in square-wave electric fields and undulated sine-function ones in sine-wave fields. Detailed study reveals how the dendrimer and condensed ions oscillate in the electric fields, which result in polarization of the molecule. To effect a significant deformation of the dendrimer, the applied field amplitude must be larger than some critical strength Ecrit and the field frequency smaller than a threshold fcrit. The response behavior is characterized by two relaxation times in square-wave fields, both of which decrease linearly with the strong field strength larger than Ecrit. In sine-wave fields, the molecular size exhibits interesting hysteretic behavior in plotting the curves with the field variation. A Maxwell-Wagner type polarization theory is derived and proved by simulations, which connects fcrit with the strength of the applied electric field.
进行朗之万动力学模拟,以研究3:1盐溶液中带电树枝状大分子在交变电场中的响应。分子尺寸的时间演化呈现出呼吸特性,在方波电场中表现为锯齿状模式,在正弦波电场中表现为起伏的正弦函数模式。详细研究揭示了树枝状大分子和凝聚离子在电场中如何振荡,这导致了分子的极化。为了使树枝状大分子发生显著变形,施加的场振幅必须大于某个临界强度Ecrit,且场频率小于阈值fcrit。响应行为在方波电场中由两个弛豫时间表征,当强场强度大于Ecrit时,这两个弛豫时间均随场强线性减小。在正弦波电场中,在绘制分子尺寸随场变化的曲线时,分子尺寸呈现出有趣的滞后行为。推导并通过模拟证明了一种麦克斯韦 - 瓦格纳型极化理论,该理论将fcrit与施加电场的强度联系起来。