• 主题
高级搜索  >
历史搜索 清空历史
首页> 外文期刊>The Journal of Chemical Physics >Transition probabilities for the Au (~2S, ~2D, and ~2P) with SiH_4reaction
【24h】

Transition probabilities for the Au (~2S, ~2D, and ~2P) with SiH_4reaction

机译：具有SiH_4反应的Au（〜2S，〜2D和〜2P）的跃迁几率

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

Transition probabilities on the interaction of the ground and the lowest excited states of gold Au(~2S :5d~(10)6s~1, ~2D: 5d~96s~2, and ~2P :5d~(10)6p~1)with silane (SiH_4) are studied throughab initioHartree-Fock self-consistent field calculations, where the atom's core is represented by relativistic effectivecore potentials. These calculations are followed by a multiconfigurational self-consistent field study.The correlation energy is accounted for through extensive variational and perturbative second ordermultireference Moller–Plesset configuration interaction analysis of selected perturbations obtained by iterative process calculations using the CIPSI program package. It is found that the Au atom in the(~2P :5d~(10)6p ~1) state inserts in the Si–H bond. In this interaction its corresponding D ~2A' potential energy surface is initially attractive and only becomes repulsive after encountering an avoidedcrossing with the initially repulsive C ~2A' surface linked to the Au(~2D:5d~96s~2)-SiH_4fragments. TheA, B, and C 2A' curves derived from the Au(~2D : 5d~96s~2) atom interaction with silane are initially repulsive, each one of them showing two avoided crossings, while the A ~2A' curve goes sharplydownwards until it meets the X ~2A' curve interacting adiabatically, which is linked with the Au(~2S :5d~(10)6s~1)-SiH_4moieties. The A2A' curve becomes repulsive after the avoided crossing withthe X ~2A', curve. The lowest-lying X ~2A' potential leads to the HAuSiH_3X intermediate molecule. This intermediate molecule, diabatically correlated with the Au(~2P:5d~(10)6p~1)+SiH_4system which lies 3.34 kcal/mol above the ground state reactants, has been carefully characterizedas have the dissociation channels leading to the AuH+SiH3 and H+AuSiH3 products. Theseproducts are reached from the HAuSiH_3intermediate without any activation barrier. The Au– SiH_4 calculation results are successfully compared to experiment. Landau–Zener theory of avoidedcrossings is applied to these interactions considering the angle θ instead of the distance r as the reaction coordinate.
机译：金和金的最低激发态相互作用的跃迁几率Au（〜2S：5d〜（10）6s〜1，〜2D：5d〜96s〜2，〜2P：5d〜（10）6p〜1硅烷（SiH_4）是通过从头算Hartree-Fock自洽场计算研究的，其中原子的核由相对论有效核势表示。这些计算之后是多配置自洽实地研究。通过使用CIPSI程序包通过迭代过程计算获得的选定扰动的广泛变分和扰动二阶多参考Moller-Plesset配置相互作用分析来考虑相关能量。发现（〜2P：5d〜（10）6p〜1）状态的Au原子插入Si–H键中。在这种相互作用中，其对应的D〜2A'势能表面最初是吸引人的，并且仅在遇到与与Au（〜2D：5d〜96s〜2）-SiH_4片段相连的初始排斥C〜2A'表面避免交叉后才变得排斥。由Au（〜2D：5d〜96s〜2）原子与硅烷相互作用得到的A，B和C 2A'曲线最初是排斥的，每个曲线都显示出两个避免的交叉点，而A〜2A'曲线则急剧下降直到它满足绝热相互作用的X〜2A'曲线，并与Au（〜2S：5d〜（10）6s〜1）-SiH_4部分相关。在避免与X〜2A'曲线交叉之后，A2A'曲线变得排斥。最低的X〜2A'势能产生HAuSiH_3X中间分子。该中间分子与基态反应物上方3.34 kcal / mol的Au（〜2P：5d〜（10）6p〜1）+ SiH_4系统绝热相关，已被仔细表征为具有导致AuH + SiH3的解离通道和H + AuSiH3产品。这些产物是从HAuSiH_3中间体获得的，没有任何激活障碍。 Au–SiH_4的计算结果已成功与实验进行了比较。将避免交叉的Landau-Zener理论应用于这些相互作用，将角度θ而不是距离r作为反应坐标。

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