Conversions of Localized Excess Electrons and Spin States under External Electric Field: Inter-Cage Electron-transfer Isomer (C20F20)3&K2

By doping two potassium atoms among three CF cages, peanut-shaped single molecular solvated dielectron (CF)&K was theoretically presented. The triplet structures with two excess electrons individually 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 (OEEF) of -20 × 10 au (-0.1018 V/Å) or a larger one can result in both left-to-right transfers of the two excess electrons, and then releasing the OEEF can form new kind of inter-cage electron-transfer isomers (III or IV). Each triplet I ~ IV with three redox sits may be new members of mixed-valent compounds, namely, Robin-Day Class II. For electrified I of (CF)&K , the following spin states are ground state: 1) triplet state in field ranges of -120 × 10 < F < -30 × 10 au and 30 × 10 < F < 111 × 10 au; 2) CS singlet state in range of F ≥ 111 × 10 and ≤ -120 × 10 au; 3) OS singlet state in ranges of -30 × 10 ≤ F ≤ -5 × 10 au and 5 × 10 ≤ F ≤ 30 × 10 au.