Ab Initio Calculation of the Lowest Singlet and Triplet Excited States of the N2 Molecule

Abstract

Ab initio calculations of the adiabatic potential curves and matrix elements of radial nonadiabatic coupling of the N₂ molecule for the states related to dissociation limits I–V were performed. The most important spectral characteristics of the adiabatic states agreed well with the available experimental and theoretical data. The diabatic states were constructed. The diabatic quantum defects and radial matrix elements of the configuration interaction of the dissociative and Rydberg configurations whose states converge to the ground state \(X^{2}\Sigma{_g^+}\) and the first electronically excited state A²Π_u of the \(\rm{N_2^+}\) ion were calculated. The possibility of using the results for calculating the cross sections and rate constants of dissociative recombination and associative ionization within the framework of the multichannel quantum defect theory was discussed.