Conversions of localized excess electrons and spin states under external electric field: Inter‐cage electron‐transfer isomer (C20F20)3&K2

Abstract

AbstractBy doping two potassium atoms among three C20F20 cages, peanut‐shaped single molecular solvated dielectron (C20F20)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 (C20F20)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.