Unique Solvated Electron State and Its Remarkable Enhancement Effect on Internuclear J -Couplings in Fluorocarbon Cage Electron Clathrates

作者：Suqing Wu, Lijuan Xue, Yuxiang Bu · 发表于：The Journal of Physical Chemistry C · 年份：2022 · DOI：10.1021/acs.jpcc.1c10587 · 被引用次数：7 · 研究领域：Advanced Chemical Physics Studies、Quantum, superfluid, helium dynamics、Atomic and Molecular Physics

Fluorocarbon cages are a type of promising excess electron carriers. Trapping of electrons in such cages, forming solvated electrons or dielectrons (e m sol m–, m = 1 and 2), not only modifies their electronic properties and energy band structures but also brings unique distributions of e m sol m–, which affect the nuclear spin properties, thus foreshadowing promising potential applications. In this work, we computationally unveil how e m sol m– govern the indirect nuclear spin–spin couplings ( N(me) J FF ) between two arbitrary F atoms in the fluorocarbon cage electron clathrates, e m @C n F n ( n = 20–60). Results indicate that the trapped electron(s) mainly reside in the cage as e m sol m– but with a reverse 2s-orbital (rev-2s) character distribution due to the permeation of e m sol m– into the carbon skeleton (bonding) and C–F (anti-bonding) bond regions. Such a rev-2s distribution not only creates a through solvated electron (TSE) coupling channel but also improves the traditional through bond (TB) and through space (TS) channels, thus governing N(me) J FF . Interestingly, e m sol m– cause J FF to present a quasi-hemisphere regularity due to the cooperation and competition of the TSE and TS + TB channels. Taking a given F atom on the cage as a pole and its sphere center angle (∠F⊗F = ca. 80°; ⊗, the cage center) line as the “quasi-equator”, where N(me) J FF = 0, if two F atoms are on the same hemisphere, their N(me) J FF is negative and | N(me) J FF | has a negative corr...