B12Fn0/− (n = 1–6) series: when do boron double chain nanoribbons become global minima?,Physical Chemistry Chemical Physics

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B12Fn0/− (n = 1–6) series: when do boron double chain nanoribbons become global minima?
Physical Chemistry Chemical Physics ( IF 2.9 ) Pub Date : 2017-11-07 00:00:00 , DOI: 10.1039/c7cp05658c
Hui Bai _{1,

2,

3} , Bing Bai _{1,

2,

3} , Lin Zhang _{1,

2,

3} , Wei Huang _{1,

2,

3} , Hua-Jin Zhai _{3,

4,

5} , Si-Dian Li _{3,

4,

5}

Affiliation

We present an extensive density-functional and wave function theory study of partially fluorinated B₁₂F_n^0/− (n = 1–6) series, which show that the global minima of B₁₂F_n^0/− (n = 2–6) are characterized to encompass a central boron double chain (BDC) nanoribbon and form stable BF₂ groups at the corresponding BDC corner when n ≥ 3, but the B₁₂F^0/− system maintains the structural feature of the well-known quasi-planar C_3v B₁₂. When we put the spotlight on B₁₂F₆^0/− species, our single-point CCSD(T) results unveil that albeit with the 3D icosahedral isomers not being their global minima, C₂ B₁₂F₆ (6.1, ¹A) and C₁ B₁₂F₆⁻ (12.1, ²A) as typical low-lying isomers are 0.60 and 1.95 eV more stable than their 2D planar counterparts D_3h B₁₂F₆ (6.7, ¹A′) and C_2v B₁₂F₆⁻ (12.7, ²A₂), respectively, alike to B₁₂H₆^0/− species in our previous work. Detailed bonding analyses suggest that B₁₂F_n^0/− (n = 2–5) possess ribbon aromaticity with σ plus π double conjugation along the BDC nanoribbon on account of their total number of σ and π delocalized electrons conforming the common electron configuration (π²⁽ⁿ⁺¹⁾σ²ⁿ). Furthermore, the simulated PES spectra of the global minima of B₁₂F_n⁻ (n = 1–6) monoanions may facilitate their experimental characterization in the foreseeable future. Our work provides new examples for ribbon aromaticity and powerful support for the F/H/Au/BO analogy.

中文翻译：

B ₁₂ F _n^{0 /-}（n = 1-6）系列：硼双链纳米带什么时候成为全局极小值？

我们对部分氟化的B ₁₂ F _n^{0 /-}（n = 1–6）系列进行广泛的密度泛函和波函数理论研究，结果表明B ₁₂ F _n^{0 /-}（n = 2– 6）的特征在于为包括中央硼双链（BDC）纳米带和形成稳定的BF _2个基团在相应的BDC角落时ñ ≥3，但B ₁₂ ˚F ^{0 / -}系统维持公知准的结构特征-平面C _3v B ₁₂。当我们将注意力放在B ₁₂ F上时₆^{0 / -}物种，我们的单点CCSD（T）的结果揭示该尽管与3D二十面体的异构体不是他们的全局最小值， c ^ ₂乙₁₂ ˚F₆（ 6.1，^1名A）和c ^ ₁乙₁₂ ˚F₆^-（ 12.1，² A）作为典型的低洼异构体比它们的2D平面对应物0.60和1.95 eV的更稳定ð _3H乙₁₂ ˚F₆（ 6.7，^1个A'）和C ^ _2V乙₁₂ ˚F₆^-（ 12.7，²甲₂），分别都至B₁₂ ħ₆^{0 / -}种在我们以前的工作。详细的键合分析表明，由于B₁₂ F_n^{0 /-}（ n = 2–5）沿BDC纳米带具有σ加π双共轭的带芳族芳香性，这是因为它们的σ和π局域电子总数符合常见电子构型（ π^{2（ñ 1）} σ^{2 ñ}）。此外，B中的全局最小值的模拟PES光谱₁₂ ˚F_ñ^-（ Ñ= 1–6）单阴离子可以在可预见的将来促进其实验表征。我们的工作提供了色带芳香性的新示例，并为F / H / Au / BO类比提供了有力的支持。

更新日期：2017-11-22

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