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Title: Mo 6 S 3 Br 6 : An Anisotropic 2D Superatomic Semiconductor
Award ID(s):
1751949
PAR ID:
10174868
Author(s) / Creator(s):
; ; ; ; ; ; ; ; ; ; ;
Publisher / Repository:
Wiley
Date Published:
Journal Name:
Advanced Functional Materials
Volume:
29
Issue:
33
ISSN:
1616-301X
Page Range / eLocation ID:
1902951
Format(s):
Medium: X
Sponsoring Org:
National Science Foundation
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  2. Anions formed by the perhalobenzene series C$$_6$$Cl$$_{n}$$F$$_{6-n}$$ ($n=0-6$) are studied computationally. All members of the series form both stable valence and stable non-valence anions. At the geometry of the neutral parents, only non-valence anions are bound, and the respective vertical electron affinities show values in the $20$ to $60$meV range. Valence anions show distorted non-planar structures, and one can distinguish two types of conformers. A-type conformers show puckered-ring structures and excess electrons delocalized over several C-Cl bonds [in case of C$$_6$$F$$_6^-$$, C-F bonds], while B-type conformers possess excess electrons essentially localized in a single C-Cl bond, which is accordingly strongly stretched and bent out-of-plane. For a specific anion, all conformers are close in energy (relative energies of less than $10$kJ/mol) and are connected by low-lying transition states. Accordingly, A-type and B-type conformers possess similar adiabatic electron affinities, however, their vertical detachment energies exhibit drastically different values, which should ease conformer distinction in photoelectron spectroscopy. 
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