Dipole-Bound Anions of Intramolecular Complexes

• Published in: The journal of physical chemistry letters 2018-03, Vol.9 (6), p.1284-1289
• Main Authors: Belogolova, Elena F, Liu, Gaoxiang, Doronina, Evgeniya P, Ciborowski, Sandra M, Sidorkin, Valery F, Bowen, Kit H
• Format: Article
• Language: English
• ISSN: 1948-7185; 1948-7185
• DOI: 10.1021/acs.jpclett.8b00355

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 –.