ISSN:
0020-7608
Keywords:
Computational Chemistry and Molecular Modeling
;
Atomic, Molecular and Optical Physics
Source:
Wiley InterScience Backfile Collection 1832-2000
Topics:
Chemistry and Pharmacology
Notes:
Several computational approaches, including Gaussian-2 (G2) and nonlocal density functional theory (DFT-GGA ), have been used to calculate the energy requirements for (a) H2N—NO2 dissociation (through N—N bond scission), (b) inversion of the amine group, and (c) isomerization through the nitro-nitrite rearrangement. Taking zero-point energies into account, the G2 predictions are 53.6 kcal/mole for the dissociation energy and 1.5 kcal/mole for the inversion barrier. The corresponding DFT-QGA values are 48.4 and 0.9 kcal/mole, and an activation energy of 48.7 kcal/mole for the nitro-nitrite rearrangement. The DFF-OGA results indicate that dissociation and rearrangement should be competitive for H2N-NO2. The same conclusion was reached earlier by Saxon and Yoshimine on the basis of MRCISD/6-3lG* calculations, although their computed energy requirements differ from the present ones by approximately 8 kcal/mole. © 1992 John Wiley & Sons, Inc.
Additional Material:
7 Tab.
Type of Medium:
Electronic Resource
URL:
http://dx.doi.org/10.1002/qua.560440845
