On delicate balance between formation and decay of tetracyanoethylene molecular anion triggered by resonance electron attachment

• Published in: The Journal of chemical physics Vol. 158; no. 16
• Main Authors: Pshenichnyuk, Stanislav A, Asfandiarov, Nail L, Rakhmeyev, Rustam G, Safronov, Aleksey M, Komolov, Alexei S
• Format: Journal Article
• Language: English
• Published: United States 28.04.2023
• ISSN: 1089-7690
• DOI: 10.1063/5.0149262

Low-energy (0-15 eV) resonance electron interaction with isolated tetracyanoethylene (TCNE) molecules is studied in vacuo by means of dissociative electron attachment (DEA) spectroscopy. Despite this molecule being relatively small, the long-lived molecular anions TCNE- are formed not only at thermal electron energy via a vibrational Feshbach resonance mechanism but also via shape resonances with the occupation of the π4* and π5* molecular orbitals by an incident electron. Dissociative decays of TCNE- are mostly observed at incident electron energy above the π7* temporary anion state predicted to lie at 1.69 eV by means of B3LYP/6-31G(d) calculations combined with the empirical scaling procedure. Electron attachment to the π6* orbital (predicted at 0.85 eV) leads to the generation of long-lived TCNE- species, which can decay via two competing processes: extra electron detachment, which appears in hundreds of microseconds, or elimination of two cyano groups to form the [TCNE - 2(CN)]- negative fragment on a tens of microsecond timescale. The latter is accompanied by the generation of a highly toxic cyanogen molecule as a neutral counterpart. Since the electron transfer to the acceptor molecule TCNE plays a key role in the formation of single-molecule magnets, the present data are of importance to understand the long-term behavior and likely harmful effects produced by cyanide-based prospective materials.