Chen G, Jena P, Kawazoe Y
Department of Physics, Virginia Commonwealth University, Richmond, Virginia 23284, USA.
J Chem Phys. 2008 Aug 21;129(7):074305. doi: 10.1063/1.2969108.
Using first-principles calculations based on gradient corrected density functional theory, we have studied the interaction of NH(3), H(2), and O(2) with Ti-benzene complexes [Ti(Bz)(2) and Ti(2)(Bz)(2)]. The energy barriers as the gas molecules approach the Ti-benzene complexes as well as the geometries of the ground state of these interacting complexes were obtained by starting with several initial configurations. While NH(3) and H(2) were found to physisorb on the Ti(Bz)(2) complex, the O(2) reacts with it strongly leading to dissociative chemisorption of the oxygen molecule. In contrast all the gas molecules react with the Ti(2)(Bz)(2) complex. These studies indicate that the reaction of certain, but not all, gas molecules can be used to probe the equilibrium geometries of organometallic complexes. Under special conditions, such as high pressure, the Ti atom intercalated between benzene molecules in Ti(Bz)(2) and the Ti(2)(Bz)(2) complexes could store hydrogen in chemisorbed states. The results are compared to available experimental data.
基于梯度校正密度泛函理论的第一性原理计算，我们研究了NH₃、H₂和O₂与钛 - 苯配合物[Ti(Bz)₂和Ti₂(Bz)₂]的相互作用。通过从几种初始构型开始，获得了气体分子接近钛 - 苯配合物时的能垒以及这些相互作用配合物基态的几何结构。虽然发现NH₃和H₂物理吸附在Ti(Bz)₂配合物上，但O₂与之强烈反应，导致氧分子的解离化学吸附。相比之下，所有气体分子都与Ti₂(Bz)₂配合物反应。这些研究表明，某些但不是所有气体分子的反应可用于探测有机金属配合物的平衡几何结构。在特殊条件下，如高压下，Ti(Bz)₂和Ti₂(Bz)₂配合物中插入苯分子之间的Ti原子可以化学吸附状态储存氢。将结果与现有的实验数据进行了比较。
