论文标题
指控迁移的监管调节
Attochemistry Regulation of Charge Migration
论文作者
论文摘要
电荷迁移（CM）是一个连贯的attosent过程，涉及局部孔跨分子的运动。为了确定分子的结构与它所表现出的CM动力学之间的关系，我们使用实时依赖时间依赖性密度功能理论对Para功能化的溴苯分子（X-C $ _6 $ H $ _4 $ -R）进行系统研究。我们通过模拟快速强场电离来启动价电子动力学，从而导致溴原子上的局部孔。所得的CM按1 fs的顺序订购，是通过X定位于c $ _6 $ _6 $ h $ _4 $定位为r局部机制的X发生的。有趣的是，对受体功能组的孔对比随着电子捐赠强度的增加而增加。该趋势由该组的Hammett Sigma值很好地描述，该趋势是量化功能化对苯衍生物化学反应性的影响的常用度量。这些结果表明，可以使用简单的口径原理和基于密度的图片来预测和理解CM。
Charge migration (CM) is a coherent attosecond process that involves the movement of localized holes across a molecule. To determine the relationship between a molecule's structure and the CM dynamics it exhibits, we perform systematic studies of para-functionalized bromobenzene molecules (X-C$_6$H$_4$-R) using real-time time-dependent density functional theory. We initiate valence-electron dynamics by emulating rapid strong-field ionization leading to a localized hole on the bromine atom. The resulting CM, which takes on the order of 1 fs, occurs via an X localized to C$_6$H$_4$ delocalized to R localized mechanism. Interestingly, the hole contrast on the acceptor functional group increases with increasing electron donating strength. This trend is well-described by the Hammett sigma value of the group, which is a commonly used metric for quantifying the effect of functionalization on the chemical reactivity of benzene derivatives. These results suggest that simple attochemistry principles and a density-based picture can be used to predict and understand CM.
