Negative ion photoelectron spectroscopy of P2N3–: electron affinity and electronic structures of P2N3˙

摘要

We report here a negative ion photoelectron spectroscopy (NIPES) and ab initio study of the recently synthesized planar aromatic inorganic ion P2N3^–, to investigate the electronic structures of P2N3^– and its neutral P2N3˙ radical. The adiabatic detachment energy of P2N3^– (electron affinity of P2N3˙) was determined to be 3.765 ± 0.010 eV, indicating high stability for the P2N3^– anion. Ab initio electronic structure calculations reveal the existence of five, low-lying, electronic states in the neutral P2N3˙ radical. Calculation of the Franck–Condon factors (FCFs) for each anion-to-neutral electronic transition and comparison of the resulting simulated NIPE spectrum with the vibrational structure in the observed spectrum allows the first four excited states of P2N3˙ to be determined to lie 6.2, 6.7, 11.5, and 22.8 kcal mol^–1 above the ground state of the radical, which is found to be a 6π-electron, ²A₁, σ state.