• 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 >Charge-Sensitive Cluster-pi Interactions Cause Altered Reactivity of Al-n(+/-,0) Clusters with Benzene: Enhanced Stability of Al(13)(+)Bz
【24h】

Charge-Sensitive Cluster-pi Interactions Cause Altered Reactivity of Al-n(+/-,0) Clusters with Benzene: Enhanced Stability of Al(13)(+)Bz

机译：电荷敏感的簇-PI相互作用会导致苯（+/-，0）簇的改变反应性：增强Al（13）（+）BZ的稳定性

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

Utilizing the homemade reflection time-of-flight mass spectrometer (Re-TOFMS), here we report a comprehensive study of the reactivity of aluminum clusters Al-n(+/-,0) with molecular benzene in the gas-phase flow tube reactor. During the reactions with benzene, Al-n(+) clusters were found to be relatively more reactive than Al-n(0/-), and interestingly, the Al-13(+) cluster exhibited more reaction product than its neighboring clusters. With an emphasis on Al-13(+/-,0) clusters, we have performed an in-depth study utilizing DFT calculations to unravel the diverse reactivity of aluminum clusters with benzene. It is revealed that the Al(13)(+)Bz cluster has a short Al-C distance and high binding energy, as well as an enlarged HOMO-LUMO gap in comparison with that of Al-13(+). This contrasts with Al-13(0/-) and Al-15(+) of which the HOMO-LUMO gaps are reduced when the cluster binds with a benzene molecule. Further, the cluster-pi interactions between aluminum clusters and benzene are fully demonstrated via topological analysis, natural bonding orbital (NBO) analysis, and noncovalent interaction plots based on independent gradient model (IGM). The unique gyro-like structure of Al-13(+) and cluster-pi interaction induce uneven redistribution of charges on the 13- atoms of Al-13(+), enabling a tight Al-C bond with strong electrostatic attraction and orbital interactions, which largely differs from the weak orbital overlap and electrostatic repulsion between benzene molecule and Al(13)(0/- )clusters.
机译：利用自制反射时间谱仪（RE-TOFM），在这里，我们报告了气相流管反应器中分子苯的铝簇Al-N（+/-，0）的反应性的综合研究。在用苯的反应期间，发现Al-N（+）簇的反应性比Al-N（0 / - ），有趣的是，Al-13（+）簇比其相邻的簇表现出更多的反应产物。强调Al-13（+/-，0）簇，我们进行了利用DFT计算的深入研究，以解开铝簇与苯的不同反应性。揭示Al（13）（+）BZ簇具有短的Al-C距离和高结合能，以及与Al-13（+）相比的扩大的Homo-Lumo间隙。这与Al-13（0 / - ）和Al-15（+）对比，其中当簇与苯分子结合时，均外腔隙间隙降低。此外，通过拓扑分析，基于独立梯度模型（IgM）的拓扑分析，天然键合轨道（NBO）分析和非共价相互作用图来完全证明铝簇和苯之间的簇-PI相互作用。 Al-13（+）和簇-PI相互作用的独特陀螺结构诱导al-13（+）13-原子上的电荷再分布，使得具有强烈的静电吸引力和轨道相互作用的紧密的Al-C键，这与苯分子和Al（13）（0 / - ）簇之间的弱轨道重叠和静电排斥不同。

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