Charge-Sensitive Cluster-π Interactions Cause Altered Reactivity of Aln±,0 Clusters with Benzene: Enhanced Stability of Al13+Bz.,The Journal of Physical Chemistry A

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Charge-Sensitive Cluster-π Interactions Cause Altered Reactivity of Aln±,0 Clusters with Benzene: Enhanced Stability of Al13+Bz.
The Journal of Physical Chemistry A ( IF 2.7 ) Pub Date : 2020-05-12 , DOI: 10.1021/acs.jpca.0c02350
Mengzhou Yang _{1,

2} , Hanyu Zhang _{1,

2} , Yuhan Jia _{1,

2} , Baoqi Yin _{1,

2} , Zhixun Luo _{1,

2}

Affiliation

Utilizing the homemade reflection time-of-flight mass spectrometer (Re-TOFMS), here we report a comprehensive study of the reactivity of aluminum clusters Aln±,0 with molecular benzene in the gas-phase flow tube reactor. During the reactions with benzene, Aln+ clusters were found to be relatively more reactive than Aln0/-, and interestingly, the Al13+ cluster exhibited more reaction product than its neighboring Aln+ clusters. With an emphasis on Al13±,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 Al13+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 Al13+. This contrasts with Al130/- and Al15+, of which the HOMO-LUMO gaps are reduced when the cluster binds with a benzene molecule. Further, the cluster-π 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 Al13+ and cluster-π interaction induce uneven redistribution of charges on the 13- atoms of Al13+, 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 Al130/- clusters.

中文翻译：

电荷敏感的团簇π相互作用会导致Aln±，0团簇与苯的反应性发生改变：Al13 + Bz的稳定性增强。

本文利用自制的反射飞行时间质谱仪（Re-TOFMS），对气相流管反应器中铝簇Aln±，0与分子苯的反应性进行了全面研究。在与苯的反应过程中，发现Aln +团簇比Aln0 /-具有更高的反应活性，有趣的是，Al13 +团簇比其相邻的Aln +团簇具有更多的反应产物。我们着重研究Al13±，0团簇，利用DFT计算进行了深入研究，以揭示铝团簇与苯的不同反应性。结果表明，与Al13 +相比，Al13 + Bz团簇具有较短的Al-C距离和较高的结合能，并且具有较大的HOMO-LUMO间隙。这与Al130 /-和Al15 +形成对比，当簇与苯分子结合时，其中的HOMO-LUMO间隙减小。此外，通过拓扑分析，自然键合轨道（NBO）分析和基于独立梯度模型（IGM）的非共价相互作用图，充分证明了铝簇与苯之间的簇-π相互作用。Al13 +的独特陀螺状结构和簇π相互作用引起Al13 +的13-原子上电荷的不均匀重新分布，从而实现具有强静电吸引和轨道相互作用的紧密Al-C键，这与弱的轨道重叠和苯分子与Al130 /-团簇之间的静电排斥。自然键合轨道（NBO）分析以及基于独立梯度模型（IGM）的非共价相互作用图。Al13 +的独特陀螺状结构和簇π相互作用引起Al13 +的13-原子上电荷的不均匀重新分布，从而实现具有强静电吸引和轨道相互作用的紧密Al-C键，这与弱的轨道重叠和苯分子与Al130 /-团簇之间的静电排斥。自然键合轨道（NBO）分析以及基于独立梯度模型（IGM）的非共价相互作用图。Al13 +的独特陀螺状结构和簇π相互作用引起Al13 +的13-原子上电荷的不均匀重新分布，从而实现具有强静电吸引和轨道相互作用的紧密Al-C键，这与弱的轨道重叠和苯分子与Al130 /-团簇之间的静电排斥。

更新日期：2020-04-30

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