Mr. Manaa et Le. Fried, DFT and ab initio study of the unimolecular decomposition of the lowest singlet and triplet states of nitromethane, J PHYS CH A, 102(48), 1998, pp. 9884-9889
The fully optimized potential, energy curves for the unimolecurar decomposi
tion of the lowest singlet and triplet states of nitromethane through the C
-NO2 bond dissociation pathway are calculated using various DFT and high-le
vel ab initio electronic structure methods. We perform gradient corrected d
ensity functional theory (DFT) and multiconfiguration self-consistent field
(MCSCF) to conclusively demonstrate that the triplet state of nitromethane
is bound. The adiabatic curve of this state exhibits a 33 kcal/mol energy
barrier as determined at the MCSCF level. DFT methods locate this barrier a
t a shorter C-N bond distance with 12-16 kcal/mol lower energy than does MC
SCF. In addition to MCSCF and DFT, quadratic configuration interactions wit
h single and double substitutions (QCISD) calculations are also performed f
or the singlet curve. The potential energy profiles of this state predicted
by DFT methods based on Becke's 1988 exchange functional differ by as much
as 17 kcal/mol from the predictions of MCSCF and QCISD in the vicinity of
the equilibrium structure. The computational methods predict bond dissociat
ion energies 5-9 kcal/mol lower than the experimental value. DFT techniques
based on Becke's 3-parameter exchange functional show the best overall agr
eement with the higher level methods.