Computed lifetimes of metastable states of the NO2+ dication

Abstract

Based on the ab initio potential energy, spin-orbit coupling, electronic transition dipole moment, and radial nonadiabatic coupling functions, the energy level positions, lifetimes, and radiative transition probabilities (Einstein A coefficients) have been determined for the lowest electronic states of NO2+ using the log-amplitude-phase, stabilization, and complex-scaling methods. The calculated characteristics are in reasonable agreement to the available experimental data, thus, evidencing the reliability of the theoretical predictions for the characteristics unobserved to date. With the exception of the v<or=2 vibrational states of the B 2Sigma+ electronic state, the calculated radiative lifetimes of the excited electronic states are longer than their predissociation lifetimes, hence, accounting for the failure of the attempts which have been made so far to observe any emission from the latter states.

Electronic state selectivity in dication-molecule single electron transfer reactions: NO2+ + NO

“…Thus, it seems clear that the excited capture and ejection NO + ions from the SET process are formed in a much wider distribution of electronic states than simply the c 3 P and B 01 S + states which are the main states populated via dissociative photoionization in this energy regime. The small changes in the equilibrium bond distance [40][41][42] between the ground electronic states of NO and NO 2+ mean the much wider range of electronic states of NO + populated in the SET reactions, in comparison with photoionization, should not result from markedly different Franck-Condon factors for forming the accessible NO + states in the capture process. However, lack of selectivity in the populated states of NO + is not surprising given the large number of predissociative and dissociative states of NO + that are accessible to NO + ions formed from the capture and ejection processes.…”

The diatomic dication PO2+

“…This arrangement is in contrast with the reverse ordering of these two lowest electronic states in the isovalent NO 2+ dication. 8 The discontinuity of the 2 2 S + PEC at ca. 5 a 0 in Fig.…”

“…[1][2][3][4][5] In a continuation of recent work on the generation of several previously unknown diatomic dications, 6,7 we report here on the formation of the PO 2+ dication, the heavy congener of the well-studied NO 2+ species. 8 The particular interest in PO 2+ is motivated by the recent observation of neutral PO in the envelope of a supergiant star, the first molecule to be detected in interstellar space with a genuine P-O bond. 9,10 In addition to the generation of PO 2+ , we have also investigated the interaction of this dication with xenon and molecular hydrogen.…”

Three-dimensional momentum imaging of dissociation in flight of metastable molecules

“…The lifetimes of these transient systems are governed by the relevant potential energy landscape and the mechanisms responsible for decay, which can include tunneling, predissociation, and radiative decay to repulsive states. Investigating the formation, properties, and decay of these metastable molecular ions experimentally and theoretically has been a prominent field of research (see review papers [10][11][12] and [13][14][15][16][17][18][19][20][21][22][23][24], for example).…”