All electron ab initio investigations of the electronic states of the MoN molecule |
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Authors: | I Shim K A Gingerich |
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Institution: | a Department of Applied Chemistry, The Technical University of Denmark, DTU 375, DK2800 Lyngby, Denmark b Department of Chemistry, Texas A & M University, College Station, TX 77843, USA |
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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∑?, 2Γ, 2Δ, and 2∑+ are found to be lower lying than the 4Π 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 re=1.636 Å and ωe=1109 cm?1, and for the 4∏ state as re=1.662 Å and ωe=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, De, is determined as 5.17 eV, and D0 as 5.10 eV. |
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Keywords: | MoN Electronic states Spectroscopic constants Ab initio CASSCF Ab initio MRCI |
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