jp6b11919_si_001.pdf (137.67 kB)
Efficient External Electric Field Manipulated Nonlinear Optical Switches of All-Metal Electride Molecules with Infrared Transparency: Nonbonding Electron Transfer Forms an Excess Electron Lone Pair
journal contribution
posted on 2016-12-14, 00:00 authored by Hui-Min He, Ying Li, Hui Yang, Dan Yu, Si-Yi Li, Di Wu, Jian-Hua Hou, Rong-Lin Zhong, Zhong-Jun Zhou, Feng-Long Gu, Josep M. Luis, Zhi-Ru LiFocusing
on the interesting new concept of all-metal electride,
centrosymmetric molecules e–+M2+(Ni@Pb12)2–M2++e– (M
= Be, Mg, and Ca) with two anionic excess electrons located at the
opposite ends of the molecule are obtained theoretically. These novel
molecular all-metal electrides can act as infrared (IR) nonlinear
optical (NLO) switches. Whereas the external electric field (F) hardly changes the molecular structure of the all-metal
electrides, it seriously deforms their excess electron orbitals and
average static first hyperpolarizabilities (β0e(F)). For e–+Ca2+(Ni@Pb12)2–Ca2++e–, a small external electric field F = 8 × 10–4 au (0.04 V/Å) drives
a long-range excess electron transfer from one end of the molecule
through the middle all-metal anion cage (Ni@Pb12)2– to the other end. This long-range electron transfer is shown by
a prominent change of excess electron orbital from double lobes to
single lobe, which forms an excess electron lone pair and electronic
structure Ca2+(Ni@Pb12)2–Ca2++2e–. Therefore, the small external electric
field induces a dramatic β0e(F) contrast from 0 (off form)
to 2.2 × 106 au (on form) in all-metal electride molecule
Ca(Ni@Pb12)Ca. Obviously, such switching is high sensitive.
Interestingly, in the switching process, such long-range excess electron
transfer does not alter the valence and chemical bond nature. Then,
this switching mechanism is a distinct nonbonding evolution named
electronic structure isomerization, which means that such switching
has the advantages of being fast and reversible. Besides, these all-metal
electride molecules also have a rare IR transparent characteristic
(1.5–10 μm) in NLO electride molecules, and hence are
commendable molecular IR NLO switches. Therefore, this work opens
a new research field of electric field manipulated IR NLO switches
of molecular all-metal electrides.
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Excess Electron Lone Pairmiddle all-metal anion cageElectric Field Manipulated Nonlinear Optical Switchesβ 0 eIR NLO switchesall-metal electrideselectron transferNiall-metal electride moleculeAll-Metal Electride MoleculesNLO electride moleculesNonbonding Electron Transfer Formsall-metal electride moleculeschemical bond nature
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