Dipole-Bound Anions of Intramolecular Complexes,The Journal of Physical Chemistry Letters

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Dipole-Bound Anions of Intramolecular Complexes
The Journal of Physical Chemistry Letters ( IF 4.8 ) Pub Date : 2018-02-26 00:00:00 , DOI: 10.1021/acs.jpclett.8b00355
Elena F. Belogolova ₁ , Gaoxiang Liu ₂ , Evgeniya P. Doronina ₁ , Sandra M. Ciborowski ₂ , Valery F. Sidorkin ₁ , Kit H. Bowen ₂

Affiliation

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 ∼0.1 Å) of dative Si ← N bond lengths when HS and FS formed dipole-bound anions, HS^– and FS^–. Detailed computational (Franck–Condon) analyses explained the absence of vibrational features in the photoelectron spectra of HS^– and FS^–.

中文翻译：

分子内复合物的偶极结合阴离子

通常将偶极结合的分子阴离子设想为具有单个过量电子的不受干扰的中性，极性分子。我们报告了由于其偶极结合阴离子的形成而导致的硅橡胶分子内分子内结构变形的观察。使用里德堡电子转移-阴离子光电子能谱法（RET-PES）和从头计算方法（CCSD和MP2）的组合来研究1-氢-（HS）和1-氟-（FS）硅烷基和它们的偶极结合阴离子，HS ^–和FS ^–。HS ^–和FS ^–的垂直脱离能（VDE）被测得分别为48和93 meV。从头算起就可以准确地重现这些VDE值及其光电子能谱。这项工作表明配位的Si←N键长度的缩短显著（由〜0.1埃），当HS和FS形成偶极-结合的阴离子，HS ^-和FS ^-。详细的计算（Franck–Condon）分析解释了HS ^–和FS ^–的光电子光谱中不存在振动特征。

更新日期：2018-02-26

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