201 East 24th Street, Austin, TX 78712, USA.
Phys Chem Chem Phys. 2018 Jul 18;20(28):19188-19194. doi: 10.1039/c8cp02377h.
Although diamondoids are broadly studied for their fundamental properties and applications, boron-nitride-based diamondoids are scarcely explored. Here we predict the stability, electronic structure, and optical absorption spectra of six boron-nitride (BN) diamondoids with first-principles methods based on pseudopotential density functional theory and many-body perturbation methods implemented with a real-space formalism. We find that four of them are thermodynamically stable at room temperature, while B10N8H24 and B6N4H16 show thermodynamic instability in molecular dynamics simulations. With the GW approximation, we predicted the ionization energies and electron affinities of BN-diamondoids and find that the evolution of the electronic structure with size does not follow the same trend as diamondoids, owing to the unbalanced numbers of boron and nitrogen atoms. We show strong photoabsorption of BN-triamantane and BN-adamantane in the infrared and visible ranges and analyze the features of low-energy absorption by examining the characteristics of related orbitals.
虽然类金刚石在其基本性质和应用方面得到了广泛的研究，但硼氮基类金刚石却很少被探索。在这里，我们通过基于赝势密度泛函理论和基于实空间形式的多体微扰方法的第一性原理方法，预测了六种硼氮（BN）类金刚石的稳定性、电子结构和光吸收光谱。我们发现其中四种在室温下是热力学稳定的，而 B10N8H24 和 B6N4H16 在分子动力学模拟中表现出热力学不稳定性。通过 GW 近似，我们预测了 BN-类金刚石的电离能和电子亲合能，并发现电子结构随尺寸的演化并不遵循与类金刚石相同的趋势，这是由于硼和氮原子的数量不平衡所致。我们在红外和可见光范围内展示了 BN-三角烷和 BN-金刚烷的强烈光吸收，并通过检查相关轨道的特征来分析低能吸收的特征。
