• 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 >Excited State Proton Transfer Dynamics of Thioacetamide in S-2(pi pi*) State: Resonance Raman Spectroscopic and Quantum Mechanical Calculations Study
【24h】

Excited State Proton Transfer Dynamics of Thioacetamide in S-2(pi pi*) State: Resonance Raman Spectroscopic and Quantum Mechanical Calculations Study

机译：硫代乙酰胺在S-2（pi pi *）态的激发态质子转移动力学：共振拉曼光谱和量子力学计算研究

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

The photophysics and photochemistry of thioacetamide (CH3CSNH2) after excitation to the S2 electronic state were investigated by using resonance Raman spectroscopy in conjunction with the complete active space self-consistent field (CASSCF) method and density functional theory (DFT) calculations. The A-band resonance Raman spectra in acetonitrile, methanol, and water were obtained at 299.1, 282.4, 266.0, 252.7, and 245.9 nm excitation wavelengths to probe the structural dynamics of thioacetamide in the S-2 state. CASSCF calculations were done to determine the transition energies and structures of the lower-lying excited states, the conical intersection points CI(S-2/S-1) and CI(S-1/S-0), and intersystem crossing points. The structural dynamics of thioacetamide in the S2 state was revealed to be along eight Franck-Condon active vibrational modes nu(15), nu(11), nu(14), nu(10), nu(8), nu(12), nu(18), and nu(19), mostly in the CC/CS/CN stretches and the CNH8,9/CCH5,6,7/CCN/CCS in-plane bends as indicated by the corresponding normal mode descriptions. The S-2 -> S-1 decay process via the S-2/S-1 conical intersection point as the major channel were excluded. The thione-thiol photoisomerization reaction mechanism of thioacetamide via the S-2,S-FC -> S'(1,min) excited state proton transfer (ESPT) reaction channel was proposed.
机译：通过共振拉曼光谱结合完整的活性空间自洽场（CASSCF）方法和密度泛函理论（DFT）计算，研究了硫代乙酰胺（CH3CSNH2）激发至S2电子态后的光物理和光化学。在299.1、282.4、266.0、252.7和245.9 nm激发波长下获得了乙腈，甲醇和水中的A带共振拉曼光谱，以探测S-2状态下硫代乙酰胺的结构动力学。进行CASSCF计算以确定较低激发态的跃迁能和结构，圆锥形交点CI（S-2 / S-1）和CI（S-1 / S-0）以及系统间交点。硫乙酰胺在S2状态下的结构动力学被揭示为沿着八种Franck-Condon主动振动模式nu（15），nu（11），nu（14），nu（10），nu（8），nu（12） ，nu（18）和nu（19），主要在CC / CS / CN拉伸和CNH8,9 / CCH5,6,7 / CCN / CCS平面内弯曲处，如相应的正常模式描述所示。排除了通过S-2 / S-1圆锥形交点作为主要通道的S-2-> S-1衰减过程。提出了硫乙酰胺通过S-2，S-FC→S'（1，min）激发态质子转移（ESPT）反应通道的硫酮-硫醇光异构化反应机理。

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