有证据表明,轨道特异性电子转移到定向环状分子中
Beike Jia1, Jonathan Laib, R F M Lobo
1Chemistry Department and Rice Quantum Institute, Rice University, Houston, Texas 77251, USA.
Journal of the American Chemical Society
|November 15, 2002
概括
原子与光环形体的碰撞显示出取决于方向的反应性. 原子 (F) 端攻击在更高的能量下变得占主导地位,与 (Cl) 和 (Br) 不同,原子 (F) 端反应力占主导地位.
科学领域:
- 化学物理 化学物理
- 分子碰撞分子碰撞
- 反应动力学 反应动力学
背景情况:
- 了解化学反应中的分子导向效应对于控制反应途径至关重要.
- Haloforms (CHX3) 由于它们的四面体结构和不同的素替代剂,具有独特的硬质挑战.
研究的目的:
- 研究分子定向在高热 (K) 原子和定向环状体 (CF3H,CCl3H,CBr3H) 之间的电子转移反应中的作用.
- 为了确定碰撞能量如何影响首选的反应场所和产品形成.
主要方法:
- 交叉分子束技术采用面向环状分子.
- 检测一致的K+和X- (化物) 离子以分析反应产物.
- 在离子对形成值附近变化的碰撞能量 (约. 5.5 eV) 的电流.
主要成果:
- CF3H表现出显著的方向依赖性,H端攻击在F-形成的门附近受到青,在更高的能量下切换到F端主导地位.
- CCl3H和CBr3H表现出最小的固体不对称性,其中素末端更具反应性.
- 在CF3H中,电子转移到sigma(CH) 抗键轨道被观察到接近值,由CF3-离子信号表示,而在CCl3H和CBr3H中,这种途径较不活跃.
结论:
- 分子导向强烈影响CF3H中的电子转移动态,与CCl3H和CBr3H不同.
- 碰撞能量在确定反应点和主导电子转移路径 (sigma (CH) 与sigma (CX) 轨道) 中发挥着关键作用.
- 低能量的离子或分子产品的形成很可能是由新生的离子的接近性决定的.
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