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Structures, stabilities and aromatic properties of endohedrally transition metal doped boron clusters M@B22, M = Sc and Ti: a theoretical study
Physical Chemistry Chemical Physics ( IF 2.9 ) Pub Date : 2020/03/10 , DOI: 10.1039/d0cp00307g Christian A. Celaya 1, 2, 3, 4, 5 , Fernando Buendía 3, 6, 7, 8 , Alan Miralrio 8, 9, 10, 11, 12 , Lauro Oliver Paz-Borbón 3, 6, 7, 8 , Marcela Beltran 1, 2, 3, 4, 5 , Minh Tho Nguyen 13, 14, 15 , Luis E. Sansores 1, 2, 3, 4, 5
Physical Chemistry Chemical Physics ( IF 2.9 ) Pub Date : 2020/03/10 , DOI: 10.1039/d0cp00307g Christian A. Celaya 1, 2, 3, 4, 5 , Fernando Buendía 3, 6, 7, 8 , Alan Miralrio 8, 9, 10, 11, 12 , Lauro Oliver Paz-Borbón 3, 6, 7, 8 , Marcela Beltran 1, 2, 3, 4, 5 , Minh Tho Nguyen 13, 14, 15 , Luis E. Sansores 1, 2, 3, 4, 5
Affiliation
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A genetic search algorithm in conjunction with density functional theory calculations was used to determine the lowest-energy minima of the pure B22 cluster and thereby to evaluate the capacity of its isomers to form endohedrally doped cages with two transition metal atoms M (M = Sc and Ti). An important charge transfer from metal atoms M to the boron cage takes place, stabilizing the endohedral compounds, as predicted with the genetic algorithm implemented. High-level coupled-cluster theory CCSD(T) calculations were carried out to confirm that the structures found are the lowest-energy isomers. For a deeper understanding of the doping effects and related charge transfer, the best structural motif of the B22 isomers was also determined when the bare cages are in anionic states, such as B222− and B224−. It was found that B22 has an appropriate size, geometric shape and electronic state to host the chosen metal atoms and, consequently, to form stable endohedrally doped compounds Ti@B22 (C2v, 4-Ti) and Sc@B22 (C2v, 5-Sc). The chemical bonding was analyzed in order to understand the molecular orbitals that these novel systems form. The cage aromaticity was evaluated by means of the nuclear independent chemical shift (NICS(0)iso) indices, the isochemical shielding surface (ICSSzz), the anisotropy of the current induced density (ACID) maps, and the magnetic ring current Gauge-Including Magnetically Induced Current (GIMIC) method, indicating that aromaticity plays a crucial role in the stabilization of endohedrally doped boron clusters. Finally, the thermodynamic stability of the latter, using parameters derived from density functional theory (DFT), was evaluated. Ab initio molecular dynamics (AIMD) simulations were performed to elucidate the stability, at high temperature, of the most stable endohedrally doped boron clusters 4-Ti and 5-Sc.
中文翻译：
内过渡金属掺杂硼团簇M @ B22，M = Sc和Ti的结构，稳定性和芳香性：理论研究
遗传搜索算法结合密度泛函理论计算用于确定纯B 22团簇的最低能量最小值，从而评估其异构体形成带有两个过渡金属原子M（M = Sc和Ti）。如所实现的遗传算法所预测的那样，发生了从金属原子M到硼笼的重要电荷转移，从而稳定了内面体化合物。进行了高级耦合簇理论CCSD（T）计算，以确认发现的结构是能量最低的异构体。为了更深入地了解掺杂效应和相关的电荷转移，B 22的最佳结构基序当裸笼处于阴离子状态时，例如B 22 2-和B 22 4-，还确定了异构体。发现B 22具有合适的尺寸，几何形状和电子态，可以容纳所选的金属原子，因此可以形成稳定的内he杂化合物Ti @ B 22（C 2v，4-Ti）和Sc @ B 22（C 2v，5-Sc）。为了了解这些新型系统形成的分子轨道，对化学键进行了分析。通过核独立的化学位移（NICS（0）iso）指数，等化学屏蔽表面（ICSS zz），电流感应密度的各向异性（ACID）图以及磁环电流计-包括磁感应电流（GIMIC）方法，表明芳香性在稳定过程中起着至关重要的作用内掺硼团簇。最后，使用密度泛函理论（DFT）得出的参数评估了后者的热力学稳定性。进行了从头算分子动力学（AIMD）模拟，以阐明高温下最稳定的内外杂杂硼团簇4-Ti和5-Sc的稳定性。
更新日期：2020-04-15
中文翻译：
内过渡金属掺杂硼团簇M @ B22，M = Sc和Ti的结构，稳定性和芳香性：理论研究
遗传搜索算法结合密度泛函理论计算用于确定纯B 22团簇的最低能量最小值，从而评估其异构体形成带有两个过渡金属原子M（M = Sc和Ti）。如所实现的遗传算法所预测的那样，发生了从金属原子M到硼笼的重要电荷转移，从而稳定了内面体化合物。进行了高级耦合簇理论CCSD（T）计算，以确认发现的结构是能量最低的异构体。为了更深入地了解掺杂效应和相关的电荷转移，B 22的最佳结构基序当裸笼处于阴离子状态时，例如B 22 2-和B 22 4-，还确定了异构体。发现B 22具有合适的尺寸，几何形状和电子态，可以容纳所选的金属原子，因此可以形成稳定的内he杂化合物Ti @ B 22（C 2v，4-Ti）和Sc @ B 22（C 2v，5-Sc）。为了了解这些新型系统形成的分子轨道，对化学键进行了分析。通过核独立的化学位移（NICS（0）iso）指数，等化学屏蔽表面（ICSS zz），电流感应密度的各向异性（ACID）图以及磁环电流计-包括磁感应电流（GIMIC）方法，表明芳香性在稳定过程中起着至关重要的作用内掺硼团簇。最后，使用密度泛函理论（DFT）得出的参数评估了后者的热力学稳定性。进行了从头算分子动力学（AIMD）模拟，以阐明高温下最稳定的内外杂杂硼团簇4-Ti和5-Sc的稳定性。
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