中文摘要：

基于密度泛函理论研究了非对称双笼型单分子溶剂化电子e-@C24F22（NH）2C20F18（1、2 和3）, 进一步展示了我们提出的一种新型电子异构体——（非对称型的）笼间电子迁移异构体. 1、2 和3 具有显著不同的偶极矩. 由于都存在两个氧化还原中心, 它们属于一种非金属型的新型Robin-Day II-III 分子. 对于1 和3, 额外电子分别定域在C24F22和C20F18笼里（Robin-Day II）; 对于2, 额外电子则离域于两个非对称的笼中（Robin-Day III）. 值得注意的是, 在y 轴方向上外加-0.0004和-0.0008 a.u.的临界电场（Ec）时可分别使1 的额外电子从C24F22笼中部分和全部地迁移到C20F18笼中, 即实现从1 到2 再到3 的转化; 当Ec为0.0004 a.u.时, 3 的额外电子从C20F18笼中全部迁移到了C24F22笼中, 即3 未经过2 直接转化成了1.

英文摘要：

The asymmetrical, double-cage-shaped, single molecular solvated electron compounds e-@C24F22（NH）2C20F18 （1, 2, and 3） were investigated based on density functional theory （DFT）. This work revealed a novel species of electromer consisting of asymmetrical inter-cage electron-transfer isomers. These inter-cage electron-transfer isomers belong to a new form of Robin-Day class II-III molecules. 1 and 3 are Robin-Day class II, with the excess electron inside the C24F22 and C20F18 cages respectively, while 2 is class III with the excess electron inside both cages. These electromers were found to exhibit significantly different dipole moments. The application of external electric fields of -0.0004 or -0.0008 a.u. in the y-axis direction of 1 resulted in either partial or whole transfer of the excess electron from C24F22 to C20F18, allowing conversion from 1 to 2 or 3. An Ec value of 0.0004 a.u. was determined, indicating that the excess electron can wholly transfer from the C20F18 cage to C24F22, resulting in conversion from 3 to 1 without going through 2.