Department of Chemistry, Ben Gurion University of the Negev, Beer-Sheva, 841051, Israel.
Department of Analytical Chemistry, Nuclear Research Center Negev, P.O Box 9001, Beer-Sheva, Israel.
Chemistry. 2023 Jun 27;29(36):e202300673. doi: 10.1002/chem.202300673. Epub 2023 May 3.
Many diamond properties are defined by substitutional defects (i. e., a carbon atom replaced by another element), which may involve the formation of structural isomers that can interconvert. Herein, we analysed by computational means the structure, thermodynamics, and kinetics of substitutional nitrogen, boron, and oxygen from small diamondoids up to the diamond bulk, focusing on the possibility of heavy atom quantum tunnelling rearrangement between the isomers. The large range of threshold energies and bond lengths lead to a variety of intriguing behaviours, including cage size dependent thermally activated tunnelling of nitrogen, and quantum delocalization of boron. In addition, we predict that applying an external electric field makes it possible to control the rearrangement thermodynamics and kinetics through tunnelling, which lets us hypothesize that these systems can potentially be used as atomic memory devices.
许多钻石性质是由取代缺陷（即一个碳原子被另一个元素取代）定义的，这可能涉及到结构异构体的形成，这些异构体可以相互转换。在此，我们通过计算手段分析了从小型金刚石样化合物到金刚石体的取代氮、硼和氧的结构、热力学和动力学，重点研究了异构体之间重原子量子隧穿重排的可能性。大的阈能和键长范围导致了各种有趣的行为，包括氮的笼尺寸依赖性热激活隧穿，以及硼的量子离域。此外，我们预测施加外部电场可以通过隧穿来控制重排的热力学和动力学，这使我们假设这些系统有可能被用作原子存储器件。
