Zhejiang Key Laboratory for Reactive Chemistry on Solid Surfaces, Institute of Physical Chemistry, Zhejiang Normal University, Jinhua 321004, China.
J Chem Phys. 2010 Jan 14;132(2):024715. doi: 10.1063/1.3292641.
Density functional theory calculation was performed to study the adsorption and reaction of CH(2)I(2) on Ag(111). Thermodynamically favorable reactions of CH(2)I(2) on Ag(111) are C-I bond ruptures and CH(2) coupling to form ethylene. The energy barriers for the C-I bond ruptures of chemisorbed CH(2)I(2) on Ag(111) are 0.43-0.48 eV, whereas the activation energy for the C-H bond rupture of chemisorbed CH(2) on Ag(111) is 1.76 eV. The coupling reaction barrier of neighboring chemisorbed CH(2) to form C(2)H(4) on Ag(111) was much less than those of the C-I bond ruptures of CH(2)I(2)(a) and the migration of chemisorbed CH(2) on Ag(111). The adsorption behaviors of different surface species on Ag(111) were well explained in terms of the charge density difference.
采用密度泛函理论计算研究了 CH(2)I(2)在 Ag(111)表面上的吸附和反应。CH(2)I(2)在 Ag(111)表面上发生的热力学有利反应是 C-I 键断裂和 CH(2)偶联形成乙烯。化学吸附的 CH(2)I(2)在 Ag(111)表面上 C-I 键断裂的能垒为 0.43-0.48 eV，而化学吸附的 CH(2)上 C-H 键断裂的活化能为 1.76 eV。相邻化学吸附的 CH(2)在 Ag(111)上偶联形成 C(2)H(4)的反应势垒远低于 CH(2)I(2)(a)的 C-I 键断裂和化学吸附的 CH(2)在 Ag(111)上的迁移能垒。根据电荷密度差，很好地解释了不同表面物种在 Ag(111)上的吸附行为。
