Dipole-Bound Anions of Intramolecular Complexes
| Autor: | Evgeniya P. Doronina, Kit H. Bowen, Sandra M. Ciborowski, Gaoxiang Liu, Valery F. Sidorkin, Elena F. Belogolova |
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| Rok vydání: | 2018 |
| Předmět: |
Materials science
Chemical polarity Ab initio 02 engineering and technology 010402 general chemistry 021001 nanoscience & nanotechnology 01 natural sciences Spectral line 0104 chemical sciences Bond length Crystallography Dipole Ab initio quantum chemistry methods Intramolecular force Molecule General Materials Science Physical and Theoretical Chemistry 0210 nano-technology |
| Zdroj: | The Journal of Physical Chemistry Letters. 9:1284-1289 |
| ISSN: | 1948-7185 |
| Popis: | 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 A) 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–. |
| Databáze: | OpenAIRE |
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