Conversions of localized excess electrons and spin states under external electric field: Inter‐cage electron‐transfer isomer (C20F20)3&K2. Issue 10 (2nd February 2021)

• Record Type: Journal Article
• Authors: Tang, Jia‐Min; Wang, Yin‐Feng; Tian, Qin; Liu, Xue‐Xia; Wang, Zhijun; Huang, Jiangen; Zhang, Hua‐Rong; Yang, Kai; Li, Zhi‐Ru
• Is Part Of: International journal of quantum chemistry. Volume 121:Issue 10(2021)
• Page Start: n/a
• Page End: n/a
• Publication Date: 2021-02-02
• Subjects: DFT -- excess electron -- external electric field -- inter‐cage electron‐transfer isomer -- mixed‐valent compound; Quantum chemistry -- Periodicals; 541.28
• DOI: 10.1002/qua.26614
• Languages: English
• ISSNs: 0020-7608

Abstract

Abstract: By doping two potassium atoms among three C20 F20 cages, peanut‐shaped single molecular solvated dielectron (C20 F20 )3 &K2 was presented theoretically. The triplet structure with two separated excess electrons respectively inside left and middle cages (isomers I or II ) are thermodynamically more stable than both open‐shell (OS) and close‐shell (CS) singlet ones with lone pair of excess electrons inside middle cage. Applying an oriented external electric field (×10 −4 au) of −20 or a larger one and then releasing it, left‐to‐right transfer occurs for both triplet excess electrons and a new kind of inter‐cage electron‐transfer isomers (III or IV ) forms. Triplet structures (I –IV ) with three redox sites may be new members of mixed‐valent compounds, namely, Robin‐Day Class II. For electrified I of (C20 F20 )3 &K2, the OS singlet state in small‐ranges of field strengths (−30 to −5 and 5–30), triplet one in mid‐ranges of field strengths (−120 to −30 and 30–111), and CS singlet one in large‐ranges of field strengths (≥111 and ≤−120) are, respectively, ground states. Abstract : Applying suitable oriented external electric field can result in both left‐to‐right transfers of the two excess electrons, and then releasing it can form new kind of inter‐cage electron‐transfer isomers. (C20 F20 )3 &K2 with three redox sits may be new members of mixed‐valent compounds, namely, Robin‐Day Class II.