Theoretical investigations on the d-p hybridized aromaticity, photoelectron spectroscopy and neutral salts of the LaX(2)over-bar(X=Al, Ga, In) clusters
Theoretical investigations on the d-p hybridized aromaticity, photoelectron spectroscopy and neutral salts of the LaX(2)over-bar(X=Al, Ga, In) clusters
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LaX2-(X=Al, Ga, In)簇的d-p杂化芳香性、光电子能谱和中性盐的理论研究
DOI：
10.1016/j.saa.2018.05.117
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发表时间：
2018-10-05
影响因子：
4.4
通讯作者：
Cheng, Shi-Bo
中科院分区：
文献类型：
--
作者：
Chen, Jing;Yang, Huan;Cheng, Shi-Bo
本文用密度泛函理论（DFT）计算了三原子LaX(2) over bar （X=Al, Ga, In）簇的几何结构和电子结构。各种尾迹结构和自旋态已经被尝试来确定这些掺镧金属团簇的最低能量几何形状。计算出这三个簇的基态均具有单重态多重的三角结构。通过计算分子轨道（MOs）和核无关化学位移（NICS）值，研究了bar （X=Al, Ga, In）簇上LaX(2)的芳香特性。本文的计算表明，所有这些金属簇都是双芳族的，即d-p杂化sigma和pi芳香性，这是由La原子的5d原子轨道和IIIA族元素的p轨道之间的有效重叠引起的。计算理论垂直脱离能（VDEs）来模拟团簇的光电子能谱（PES）。此外，通过将碱离子（Li+和Na+）加入到LaX(2) over bar （X=Al, Ga, In）簇中，还研究了相应中性盐的几何形状和电子结构，以获得更多关于使用这些芳香阴离子作为构建块的潜力的见解。(C) 2018 Elsevier B.V.版权所有
We present an extensive density functional theory (DFT) calculations on the geometrical and electronic structures of the triatomic LaX(2) over bar (X=Al Ga, In) clusters. Various trail structures and spin states have been attempted to determine the lowest-energy geometries of these La-doped metal clusters. The ground states of all three clusters are calculated to possess the trigonal structures with the singlet multiplicities. The calculations on molecular orbitals (MOs) and nucleus-independent chemical shift (NICS) values have been performed to examine the aromatic characteristics of the LaX(2) over bar (X=Al, Ga, In) clusters. The present calculations disclose that all these metal clusters are doubly aromatic, namely d-p hybridized sigma and pi aromaticity resulting from the effective overlap between the 5d atomic orbital of the La atom and the p orbitals of the IIIA group elements. Theoretical vertical detachment energies (VDEs) were also calculated to simulate the photoelectron spectra (PES) of the clusters. In addition, by adding the alkali cations (Li+ and Na+) into the LaX(2) over bar (X=Al, Ga, In) clusters, the geometries and electronic structures of the corresponding neutral salts have also been investigated to gain more insights in the potential of using these aromatic anions as building blocks. (C) 2018 Elsevier B.V. All rights reserved.