• 主题
高级搜索  >
历史搜索 清空历史
首页> 外文期刊>The journal of physical chemistry, A. Molecules, spectroscopy, kinetics, environment, & general theory >Photodissociation Reaction of 1,2-Diiodoethane in Solution:A Theoretical and X-ray Diffraction Study
【24h】

Photodissociation Reaction of 1,2-Diiodoethane in Solution:A Theoretical and X-ray Diffraction Study

机译：1,2-二碘乙烷在溶液中的光解离反应：理论和X射线衍射研究

获取原文
获取原文并翻译 | 示例
           
页面导航
  • 摘要
  • 著录项
  • 相似文献
  • 相关主题

摘要

Various molecular species are known to form during the photoreaction of C_2H_4I_2 in the gas phase and in solution.We have studied all species involved in this reaction by ab initio and density functional theory (DFT) calculations:Geometries,energies,and vibrational frequencies of C_2H_4I_2,bridged C_2H_4I_centre dot,anti C_2H_4I centre dot,C_2H_4,I_2,I_3~-,and the isomer C_2H_4I-I were calculated.The absorption peaks and oscillator strengths of selected species along the potential energy surface (PES) were calculated using time-dependent DFT and were compared with available experimental results.The calculated PES satisfactorily describes the observed reactions of the photoexcited C_2H_4I_2 molecule.In the gas phase,there is only one reaction pathway:the first C-I bond ruptures followed by a secondary C-I breakage in the haloethyl radical C_2H_4I centre dot.In solution,by contrast,another reaction channel,which is energetically more favored over the secondary dissociation,is switched on due to a solvation effect:the bridged C_2H_4I centre dot can bind to the free iodine atom to form a C_2H_4I-I isomer without any energy barrier.The isomer can then break into C_2H_4 and I_2.The rotational barriers in the gas phase and in solution were also calculated and compared.To provide experimental data on the structure of C_2H_4I_2 in solution,the ground state structure of C_2H_4I_2 in methanol was determined from static X-ray diffraction data using 88 keV (lambda=0.14 A) X-rays.The structural parameters are compared with those from the theoretical results.
机译：已知在气相和溶液中C_2H_4I_2的光反应过程中会形成各种分子。我们通过从头算和密度泛函理论（DFT）计算研究了参与此反应的所有物种：C_2H_4I_2的几何形状，能量和振动频率，桥连的C_2H_4I_中心点，反C_2H_4I中心点，C_2H_4，I_2，I_3〜-和异构体C_2H_4I-I的计算。沿时势面（PES）计算选定物种的吸收峰和振荡强度DFT并与可用的实验结果进行了比较。计算得出的PES令人满意地描述了光激发的C_2H_4I_2分子的观察到的反应。 C_2H_4I中心点。相比之下，溶液中的另一反应通道在能量上优于二次解离，因此切换为n由于具有溶剂化作用：桥接的C_2H_4I中心点可以与游离碘原子结合形成C_2H_4I-I异构体，而没有任何能垒，然后该异构体可以分解为C_2H_4和I_2。为了计算溶液中C_2H_4I_2的结构，提供了实验数据，使用88 keV（λ= 0.14 A）X射线从静态X射线衍射数据确定了甲醇中C_2H_4I_2的基态结构。将结构参数与理论结果进行比较。

著录项

相似文献

  • 外文文献
  • 中文文献
  • 专利
获取原文

客服邮箱：kefu@zhangqiaokeyan.com

京公网安备：11010802029741号 ICP备案号：京ICP备15016152号-6 六维联合信息科技 (北京) 有限公司©版权所有

  • 客服微信

  • 服务号