Quintet electronic states of N2

Abstract

We use large scale ab initio calculations to investigate the valence and valence-Rydberg quintet states of N(2), their transition moments and their spin-orbit couplings to the close lying triplet electronic states. In addition to the A' (5)Sigma(g)(+) and the C" (5)Pi(ui) states already known, we identify two weakly bound states (2 (5)Sigma(g)(+) and 2 (5)Pi(u)) at approximately 95,300 and 106,200 cm(-1) above N(2)(X (1)Sigma(g)(+), v=0). The other quintets are viewed to be repulsive in nature. Our potentials and couplings are used later to derive a set of accurate spectroscopic data for these quintets, their spin-orbit constants, and to elucidate the quintet-triplet dynamics and the role of these newly identified quintets for the production of cold atomic nitrogen.

Erratum: “Quantum-state Dependence of Product Branching Ratios in Vacuum Ultraviolet Photodissociation of N2” (2016, ApJ, 819, 23)

“…Therefore, a multiconfigurational approach is adopted where the electronic computations were carried out using the Complete Active Space Self Consistent Field (CASSCF; approach followed by the internally contracted Multi Reference Configuration Interaction (MRCI; ) technique as implemented in MOLPRO (Werner et al 2012). We followed the procedure established in Spelsberg & Meyer (2001), Ndome et al (2008),and Hochlaf et al (2010aHochlaf et al ( , 2010b. Briefly, the CASSCF active space is constructed by the valence molecular orbitals (MOs) of N 2 increased by one s g and one p g MOs.…”

Valence–Rydberg electronic states of N2: spectroscopy and spin–orbit couplings

“…They were widely discussed and commented in Ref. [16]. It is worth noting that the literature on the N 2 electronic states is wide and it is not the scope of the present paper to enumerate it.…”

“…Outside the FranckCondon region of GS, a quintet-quintet emitting system was detected and assigned later, by the help of theoretical calculations, to the C" 5 Π u ß A' 5 Σ g + transition, which is responsible for the Herman (HIR) bands of N 2 [9][10][11][12][13][14][15]. Very recently, some of us have predicted a second quintet-quintet system at higher energies [16]. It was shown there that some of these quintets couple to their close lying electronic states of triplet spin-multiplicities and participate into their perturbation as noticed experimentally [16][17][18][19][20][21][22][23].…”

“…Very recently, some of us have predicted a second quintet-quintet system at higher energies [16]. It was shown there that some of these quintets couple to their close lying electronic states of triplet spin-multiplicities and participate into their perturbation as noticed experimentally [16][17][18][19][20][21][22][23].…”

Computed bound and continuum electronic states of the nitrogen molecule

“…This crossing is the result of the interaction between the n = 4 Rydberg state and the valence state. In practice, one has to work very hard to use quantum chemistry packages such as MOLPRO to characterise even energetically low-lying regions containing Rydberg-valence crossings as attested by the very careful but limited study of Spelsberg and Meyer [30] and the more complete but less accurate studies of Hochlaf et al [31,32]. .…”