All electron ab initio investigations of the electronic states of the MoN molecule

Abstract

The low lying electronic states of the molecule MoN were investigated by performing all electron ab initio multi-configuration self-consistent-field (CASSCF) calculations. The relativistic corrections for the one electron Darwin contact term and the relativistic mass-velocity correction were determined in perturbation calculations. The electronic ground state is confirmed as being 4∑ − . The chemical bond of MoN has a triple bond character because of the approximately fully occupied delocalized bonding π and σ orbitals. The spectroscopic constants for the ground state and ten excited states were derived. The excited doublet states 2∑ −, 2 Γ, 2 Δ, and 2∑ + are found to be lower lying than the 4 Π state that was investigated experimentally. Elaborate multi-configuration configuration-interaction (MRCI) calculations were carried out for the states 4∑ − and 4∏ using various basis sets. The spectroscopic constants for the 4∑ − ground state were determined as r e=1.636 Å and ω e=1109 cm −1, and for the 4∏ state as r e=1.662 Å and ω e=941 cm −1. The values for the ground state are in excellent agreement with available experimental data. The MoN molecule is polar with a charge transfer from Mo to N. The dipole moment was determined as 2.11 D in the 4∑ − state and as 4.60 D in the 4∏ state. These values agree well with the revised experimental values determined from molecular Stark spectroscopic measurements. The dissociation energy, D e, is determined as 5.17 eV, and D 0 as 5.10 eV.