Gerbi Andrea, Vattuone Luca, Rocca Mario, Valbusa Ugo, Pirani Fernando, Cappelletti David, Vecchiocattivi Franco
Istituto Nazionale per la Fisica della Materia, Unità di Genova, Dipartimento di Fisica, Università di Genova, 16146 Genoa, Italy.
J Chem Phys. 2005 Dec 8;123(22):224709. doi: 10.1063/1.2136159.
The control of spatial orientation of molecules has a great influence on the stereodynamics of elementary processes occurring both in homogeneous and heterogeneous phases. Nonpolar molecules have so far escaped direct experimental investigations because of their poor sensitivity to several external constraints. Recently, it has been shown that the collisional alignment produced in supersonic expansions coupled with molecular-beam velocity selection can help solve such problems. Here we show that the sticking probability of ethylene, a nonpolar molecule prototypical of unsaturated hydrocarbons, on an O(2)-precovered Ag(001) surface is larger for molecules approaching in a helicopter-like motion than for those cartwheeling. A mechanism involving a weakly bound precursor state is suggested, with helicopter molecules having a lower chance of being scattered back into the gas phase than cartwheels when colliding with preadsorbed ethylene.
分子空间取向的控制对均相和非均相体系中发生的基本过程的立体动力学有很大影响。由于非极性分子对几种外部约束的敏感性较差,迄今为止它们尚未得到直接的实验研究。最近的研究表明,超声速膨胀中产生的碰撞取向与分子束速度选择相结合有助于解决此类问题。在此我们表明,乙烯(一种不饱和烃的典型非极性分子)在O(2)预覆盖的Ag(001)表面上的吸附概率,对于以类似直升机运动方式接近的分子而言,要高于以侧翻方式接近的分子。我们提出了一种涉及弱束缚前驱体状态的机制,即当与预吸附的乙烯碰撞时,直升机状分子比侧翻分子被散射回气相的几率更低。