Dissociation of HCl in water nanoclusters: an energy decomposition analysis perspective
Dissociation of HCl in water nanoclusters: an energy decomposition analysis perspective
复制标题
HCl 在水纳米团簇中的解离：能量分解分析视角
DOI：
10.1039/d1cp04587c
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发表时间：
2021
影响因子：
3.3
通讯作者：
Head-Gordon, Martin
中科院分区：
文献类型：
--
作者：
Zech, Alexander;Head-Gordon, Martin
如已知的，小的HCl-水纳米团簇显示出特定的解离行为，由此HCl的离子解离需要至少四个水分子。在这项工作中，我们研究如何分子间的相互作用，促进这种纳米团簇的离子解离。为此，引入了一组45个具有多达四个水分子的HCl-水纳米团簇。采用基于绝对定域分子轨道的能量分解分析（ALMO-EDA）来研究冻结相互作用、色散、极化和电荷转移对解离的重要性。垂直ALMO-EDA方案被施加到HCl-水团簇沿着质子转移坐标变化的旁观者水分子的量。相应的ALMO-EDA结果表明，只有在四个水分子的存在下，解离的集群有明显的偏好。我们的绝热ALMO-EDA结果的分析揭示了推拉机制的基础上向前和向后的电荷转移之间的协同作用的HCl键的不稳定。
As known, small HCl–water nanoclusters display a particular dissociation behaviour, whereby at least four water molecules are required for the ionic dissociation of HCl. In this work, we examine how intermolecular interactions promote the ionic dissociation of such nanoclusters. To this end, a set of 45 HCl–water nanoclusters with up to four water molecules is introduced. Energy decomposition analysis based on absolutely localized molecular orbitals (ALMO-EDA) is employed in order to study the importance of frozen interaction, dispersion, polarization, and charge-transfer for the dissociation. The vertical ALMO-EDA scheme is applied to HCl–water clusters along a proton-transfer coordinate varying the amount of spectator water molecules. The corresponding ALMO-EDA results show a clear preference for the dissociated cluster only in the presence of four water molecules. Our analysis of adiabatic ALMO-EDA results reveals a push–pull mechanism for the destabilization of the HCl bond based on the synergy between forward and backward charge-transfer.