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

Abstract

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.