Abstract
The low lying electronic states of the molecule MoN have been
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 have been
determined in perturbation calculations. The electronic ground
state is confirmed as being 4 . The chemical bond of MoN has
triple bond character due to the approximately fully occupied
delocalized bonding and orbitals. The spectroscopic constants for
the ground state and ten excited states have been derived. The
excited doublet states, 2 , 2 , 2 , and 2 + are found to be lower
lying than the 4 state that has been investigated experimentally.
Elaborate multi configuration configuration interaction (MRCI)
calculations have been carried out for the states 4 and 4 using
various basis sets. The spectroscopic constants for the 4 ground
state have been determined as re = 1.636 Å and e = 1109 cm-1, and
for the 4 state as re = 1.662 Å and e = 941 cm-1. The values for
the ground state are in excellent agreement with available
experimental data. The MoN molecule is polar with charge transfer
from Mo to N. The dipole moment has been determined as 2.11 D in
the 4 state and as 4.60 D in the 4 state. The latter value is in
excellent agreement with the experimental value determined from
molecular Stark spectroscopic measurements. The dipole moment for
the 4 state determined in the present work is 1.27 D less than the
experimental value. This suggests an reinvestigation of the
experiment. The dissociation energy, De, is determined as 5.17 eV,
and D0 as 5.10 eV.
Original language | English |
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Journal | Journal of molecular structure (Theochem) |
Volume | 460 |
Pages (from-to) | 123-136 |
Publication status | Published - 1999 |