Dipole-Bound Anions of Intramolecular Complexes
Dipole-Bound Anions of Intramolecular Complexes
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DOI：
10.1021/acs.jpclett.8b00355
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发表时间：
2018-03-15
影响因子：
5.7
通讯作者：
Bowen, Kit H.
中科院分区：
文献类型：
--
作者：
Belogolova, Elena F.;Liu, Gaoxiang;Bowen, Kit H.
偶极结合分子阴离子通常被设想为具有单个多余电子的未受扰动的中性极性分子。我们报道了硅烷分子内由于偶极结合阴离子形成的分子内结构扭曲的观察。采用Rydberg电子转移-阴离子光电子能谱（RET-PES）和从头计算方法（CCSD和MP2）相结合的方法研究了1-氢（HS）和1-氟（FS）硅烷及其偶极束缚阴离子HS-和FS-。HS-和FS-的垂直分离能（VDEs）分别为48和93 meV。从头计算精确地再现了这些VDE值以及它们的光电子谱曲线。这项工作揭示了相对Si的显著缩短（大约0.1埃）
Dipole-bound molecular anions are often envisioned as unperturbed neutral, polar molecules with single excess electrons. We report the observation of intramolecular structural distortions within silatrane molecules due to the formation of their dipole-bound anions. The combination of Rydberg electron transfer-anion photoelectron spectroscopy (RET-PES) and ab initio computational methodologies (CCSD and MP2) was used to study 1-hydro- (HS) and 1-fluoro- (FS) silatranes and their dipole bound anions, HS- and FS-. The vertical detachment energies (VDEs) of HS- and FS- were measured to be 48 and 93 meV, respectively. Ab initio calculations accurately reproduced these VDE values as well as their photoelectron spectral profiles. This work revealed significant shortening (by similar to 0.1 angstrom) of dative Si