Kumar Anmol, Gadre Shridhar R
Department of Chemistry, IIT Kanpur, Kanpur-208016, India.
Phys Chem Chem Phys. 2015 Jun 14;17(22):15030-5. doi: 10.1039/c5cp02112j.
The nature of electron localization in electrides is explored by examining their electrostatic features. Ab initio investigations of three experimentally synthesized and two theoretically modeled organic electrides are performed in order to unveil the characteristics of the trapped electron and to understand the reason for their low thermal stability. A single molecular unit of the electride extracted from the crystal structure shows an unusually deep minimum in its electrostatic potential, located far away from its van der Waals surface. A comparison of electrostatic features of the usual electron localization such as lone pairs has been drawn against those of the trapped electron in the crystal voids of electrides. Further characterization of the MESP minimum brings out the isotropic behavior of the trapped electrons as compared to the lone-pair minimum which is strongly directional. The analysis of single molecular behavior of an electride has been extended to the set of molecules in the unit cell of the crystal lattice. The present study also suggests the criteria for ligands to achieve thermally stable organic electrides.
通过研究电子化合物的静电特征来探索其中电子局域化的本质。对三种实验合成的和两种理论建模的有机电子化合物进行了从头算研究，以揭示捕获电子的特征并理解其热稳定性低的原因。从晶体结构中提取的电子化合物的单个分子单元在其静电势中显示出异常深的最小值，该最小值远离其范德华表面。已将诸如孤对等通常电子局域化的静电特征与电子化合物晶体空隙中捕获电子的静电特征进行了比较。与具有强方向性的孤对最小值相比，对MESP最小值的进一步表征揭示了捕获电子的各向同性行为。对电子化合物单分子行为的分析已扩展到晶格晶胞中的分子集合。本研究还提出了配体实现热稳定有机电子化合物的标准。
