Department of Chemistry, University of Rochester, Rochester, New York 14627, USA.
J Phys Chem A. 2009 Dec 31;113(52):15233-9. doi: 10.1021/jp905610u.
The D(+) transfer reaction between O(-) ((2)P) and D(2) to form OD and D(-) was studied using the crossed molecular beam technique at collision energies of 1.55 and 1.95 eV. The reaction appears to proceed by a direct mechanism through large impact parameters. At both collision energies, more that 70% of the excess energy is partitioned into product translation. At the lower collision energy, the OD products are formed in the ground vibrational state with a bimodal rotational energy distribution. At the higher collision energy, both v' = 0 and 1 products are formed; ground vibrational state products have a mean rotational energy of 0.05 eV, corresponding to J' approximately 6. In contrast, OD products formed in v' = 1 are formed with significant rotational excitation, with the most probable J' approximately 15. The bimodal rotational distribution is rationalized in terms of trajectories that sample two potential surfaces coupled by a conical intersection in the vicinity of the O...DD intermediate that correlate to (OD(-),D) or (OD,D(-)) products.
O(-) ((2)P)和 D(2)之间的 D(+)转移反应形成 OD 和 D(-)，使用交叉分子束技术在 1.55 和 1.95 eV 的碰撞能下进行研究。反应似乎通过大的碰撞参数通过直接机制进行。在两种碰撞能下，超过 70%的过剩能量分配给产物平移。在较低的碰撞能下，OD 产物以基频振动态形成，具有双峰旋转能量分布。在较高的碰撞能下，同时形成 v'=0 和 1 的产物；基频振动态产物具有 0.05 eV 的平均旋转能，对应于 J'约为 6。相比之下，在 v'=1 中形成的 OD 产物具有显著的旋转激发，最可能的 J'约为 15。双峰旋转分布可以根据在 O...DD中间体附近通过锥形交叉连接的两个势能面的轨迹来合理化，这些轨迹与 (OD(-),D)或 (OD,D(-))产物相关联。
