• 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 >Theoretical Analysis of Heteroaromatic Thioaminyl Radicals. Part 2: A Comparison of Ab Initio and Density Functional Methods in the Description of Redox Processes
【24h】

Theoretical Analysis of Heteroaromatic Thioaminyl Radicals. Part 2: A Comparison of Ab Initio and Density Functional Methods in the Description of Redox Processes

机译：杂芳族硫胺基自由基的理论分析。第2部分：氧化还原过程描述中从头算和密度泛函方法的比较

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

Gas-phase electron-transfer processes for 12 known thioaminyl radicals belonging to 7 general classes of heterocycles have been investigated using the HF and B3LYP methods with 6-31G(d) basis set augmented with diffuse functions. The basis set was chosen based on favorable comparison of the theoretical and experimental normal modes for 1a. The calculated ionization potentials (I_p) and free energy changes were subsequently compared with the experimental I_p and electrochemical redox potentials. It was found that the DFT method performs better than the HF method giving excellent correlations for vertical I_p and #SIGMA#~red_1/2 (R~2 > 0.98), but not for #SIGMA#~ox_1/2 or #SIGMA#_cell (R~2 = 0.7). The calculated disproportionation energies were compared with the available conductivty data for radicals showing a qualitative correlation. Generally, low dispropor-tionation energies and hence high conductivity are obtained for large #pi# systems, such as 11, containing the -N-S-S- array of heteroatoms. The established correlations provide a set of empirical scaling factors relating the calculated quantities with experimental observables for cyclic thioaminyl radicals. They were used in analysis of several radicals in the context of conductivity of molecular solids. A companion paper (ref 1) also appears in this issue.
机译：已使用HF和B3LYP方法对6-31G（d）基集增强了扩散功能的化合物，研究了属于7个普通杂环的12个已知硫胺基自由基的气相电子转移过程。基于对1a的理论和实验正常模式的有利比较来选择基础集。随后将计算出的电离电势（I_p）和自由能变化与实验I_p和电化学氧化还原电势进行比较。发现DFT方法的性能优于HF方法，从而为垂直I_p和＃SIGMA＃〜red_1 / 2（R〜2> 0.98）提供了出色的相关性，但对于＃SIGMA＃〜ox_1 / 2或＃SIGMA＃_cell却没有。 （R〜2 = 0.7）。将计算出的歧化能与自由基的可用电导率数据进行比较，从而显示出定性的相关性。通常，对于包含杂原子的-N-S-S-阵列的大型＃pi＃系统（例如11）可获得低歧化能，从而获得高电导率。所建立的相关性提供了一组经验比例因子，该比例因子将计算出的量与环硫胺基自由基的实验观测值相关联。它们在分子固体电导率的背景下用于几个自由基的分析。随附的论文（参考文献1）也出现在本期中。

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