论文标题
质子化和去质子化对电子转移介导的衰减和原子间腐烂的影响
Effect of Protonation and Deprotonation on Electron Transfer Mediated Decay and Interatomic Coulombic Decay
论文作者
论文摘要
环境中的电子激发原子或分子通常受到原子间/分子间库仑衰减（ICD）和/或电子转移介导的衰减（ETMD）机制。可能影响这些非辐射衰减机制的众多变量中的一些包括键距离，附近原子或分子的数量以及极化效应。在本文中，我们研究了质子化和去质子化对这些非辐射衰减过程中临时结合状态的电离电势（IP），双电离电位（DIP）和寿命（或衰减宽度）的影响。我们选择了lih-nh $ _3 $和lih-h $ _2 $ o作为测试系统。通过复杂的吸收电势（CAP-EOM-CCSD）增强运动耦合群集单打和双重方法的方程式已用于计算衰减状态的能量位置和系统的衰减速率。与中性系统相比，Lih-nh $ _3 $ _3 $ _3 $/lih-h $ _2 $ o要么来自金属中心（LIH）或从氨/水中降低IP和DIP。相反，与中性系统相比，质子化增加了这些数量。质子化关闭了ICD/ETMD的内价状态松弛通道。例如，O-2S/N-2S状态的衰减在质子化系统中停止（LIH $ _2^+$ - H $ _2 $ O，LIH $ _2^+$ -NH $ _3 $和LIH-NH $ _4^+$）。我们的研究还表明，可以通过质子化和去质子化来改变效率，即ICD/ETMD的速率。预计将对化学和生物系统产生影响
Electronically excited atoms or molecules in an environment are often subject to interatomic/intermolecular Coulombic decay (ICD) and/or electron transfer mediated decay (ETMD) mechanisms. A few of the numerous variables that can impact these non-radiative decay mechanisms include bond distance, the number of nearby atoms or molecules, and the polarisation effect. In this paper, we have studied the effect of protonation and deprotonation on the ionization potential (IP), double ionization potential (DIP), and lifetime (or decay width) of the temporary bound state in these non-radiative decay processes. We have chosen LiH-NH$_3$ and LiH-H$_2$O as test systems. The equation of motion coupled cluster singles and doubles method augmented by complex absorbing potential (CAP-EOM-CCSD) has been used in calculating the energetic position of the decaying state and the system's decay rate. Deprotonation of LiH-NH$_3$/LiH-H$_2$O either from the metal center (LiH) or from ammonia/water lowers the IP and DIP compared to the neutral systems. In contrast, protonation increases these quantities compared to neutral systems. The protonation closes the inner valence state relaxation channels for ICD/ETMD. For example, the decay of the O-2s/N-2s state stops in protonated systems (LiH$_2^+$-H$_2$O, LiH$_2^+$-NH$_3$, and LiH-NH$_4^+$). Our study also shows that the efficiency, i.e., the rate of ICD/ETMD, can be altered by protonation and deprotonation. It is expected to have implications for chemical and biological systems
