• 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 >Reactions of F+(P-3) and F+(D-1) with silicon oxide. Possibility of spin-forbidden processes
【24h】

Reactions of F+(P-3) and F+(D-1) with silicon oxide. Possibility of spin-forbidden processes

机译：F +（P-3）和F +（D-1）与氧化硅的反应。禁止旋转过程的可能性

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

High level ab initio and density functional theory calculations have been carried out to study the potential energy surfaces associated with the reactions of F+ in its P-3 ground state and in its D-1 first excited state with silicon dioxide. The structures and vibrational frequencies of the stationary points of both potential energy surfaces were obtained at the B3LYP/6-31G(d) level. Final energies were calculated at the B3LYP/6-311+G-(3df,2p) and at the G3X levels of theory. [Si, O-2, F](+) singlet and triplet state cations present very different bonding characteristics. The most favorable reactions path in F+(P-3) + SiO2 reactions should yield O-2 + SiF+, while in the reactions in the first excited state, only a charge exchange process, yielding F(P-2) + SiO2 +((2)A), should be observed. However, both potential energy surfaces cross each other, because although the entrance F+(P-3) + SiO2 lies 34.5 kcal/mol below F+(D-1) + SiO2, the global minimum of the singlet PES lies 10.3 kcal/mol below the global minimum of the triplet. The minimum energy crossing point between them is close to the global minimum, and the spin-orbit coupling is not zero, suggesting that very likely some of the products will be formed in the singlet hypersurface. The existence of instabilities and large spin-contamination in the description of some of the systems render the DFT calculations unreliable.
机译：已经进行了高级的从头算和密度泛函理论计算，以研究与F +在其P-3基态和在D-1第一激发态与二氧化硅的反应相关的势能面。在B3LYP / 6-31G（d）的水平上获得了两个势能面的固定点的结构和振动频率。最终能量以B3LYP / 6-311 + G-（3df，2p）和G3X理论水平计算。 [Si，O-2，F]（+）单线态和三线态阳离子具有非常不同的键合特性。 F +（P-3）+ SiO2反应中最有利的反应路径应为O-2 + SiF +，而在第一个激发态的反应中，只有电荷交换过程才产生F（P-2）+ SiO2 +（ （2）A），应遵守。但是，两个势能面彼此交叉，因为尽管入口F +（P-3）+ SiO2比F +（D-1）+ SiO2低34.5 kcal / mol，但单重态PES的全局最小值在10.3 kcal / mol以下三元组的全局最小值。它们之间的最小能量交叉点接近全局最小值，并且自旋轨道耦合不为零，这表明某些产物很可能在单重态超表面中形成。在某些系统的描述中，由于存在不稳定性和较大的自旋污染，因此DFT计算不可靠。

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