...
  • 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 >Parameters For Excess Electron Transfer in DNA. Estimation Using Unoccupied Kohn-Sham Orbitals and TD DFT
【24h】

Parameters For Excess Electron Transfer in DNA. Estimation Using Unoccupied Kohn-Sham Orbitals and TD DFT

机译：DNA中过量电子转移的参数。使用空空的Kohn-Sham轨道和TD DFT进行估计

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

We show that the energetics and electronic couplings for excess electron transfer (EET) can be accurately estimated by using unoccupied Kohn-Sham orbitals (UKSO) calculated for neutral π stacks. To assess the performance of different DFT functionals, we use MS-PT2 results for seven π stacks of nucleobases as reference data. The DFT calculations are carried out by using the local spin density approximation SVWN, two generalized gradient approximation functionals BP86 and BLYP, and two hybrid functionals B3LYP and BH&HLYP. Best estimations within the UKSO approach are obtained by the B3LYP and SVWN methods. TD DFT calculations provide less accurate values of the EET parameters as compared with the UKSO data. Also, the excess charge distribution in the radical anions is well described by the LUMOs of neutral systems. In contrast, spin-unrestricted DFT calculations of radical anions considerably overestimate delocalization of the excess electron. The excellent results obtained for the ground and excited states of the radical anions (excitation energy, transition dipole moment, electronic coupling, and excess electron distribution) by using UKSO of neutral dimers suggest an efficient strategy to calculate the EET parameters for DNA π stacks.
机译：我们显示，可以通过使用为中性π堆计算的未占用的科恩-沙姆轨道（UKSO）来准确估算过量电子转移（EET）的能量学和电子耦合。为了评估不同DFT功能的性能，我们将MS-PT2结果用于7个π核碱基堆栈作为参考数据。 DFT计算是通过使用局部自旋密度近似SVWN，两个广义梯度近似函数BP86和BLYP以及两个混合函数B3LYP和BH＆HLYP进行的。 UKSO方法内的最佳估计是通过B3LYP和SVWN方法获得的。与UKSO数据相比，TD DFT计算提供的EET参数的准确度较低。同样，中性系统的LUMO很好地描述了自由基阴离子中过量的电荷分布。相反，自由基阴离子的自旋无限制DFT计算大大高估了多余电子的离域。使用中性二聚体的UKSO获得的自由基阴离子的基态和激发态（激发能，跃迁偶极矩，电子耦合和过量电子分布）的优异结果表明，一种有效的策略可以计算DNAπ堆栈的EET参数。

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