Conversions of Localized Excess Electrons and Spin States under External
Electric Field: Inter-Cage Electron-transfer Isomer
(C20F20)3&K2
Abstract
By doping two potassium atoms among three
C20F20 cages, peanut-shaped single
molecular solvated dielectron
(C20F20)3&K2
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 × 10-4 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
(C20F20)3&K2
, the following spin states are ground state: 1) triplet state in field
ranges of -120 × 10-4 <
Fx < -30 × 10-4 au
and 30 × 10-4 < F-4
< 111 × 10-4 au; 2) CS singlet state in
range of Fx ≥ 111 × 10-4 and ≤
-120 × 10-4 au; 3) OS singlet state in ranges of -30 ×
10-4 ≤ Fx ≤ -5 ×
10-4 au and 5 × 10-4 ≤
Fx ≤ 30 × 10-4 au.