Journal
JOURNAL OF CHEMICAL PHYSICS
Volume 132, Issue 11, Pages -Publisher
AIP Publishing
DOI: 10.1063/1.3354910
Keywords
carbon compounds; dissociation energies; molecular moments; negative ions; nitrogen; nitrogen compounds; oxygen; positive ions; potential energy surfaces; variational techniques
Funding
- FWO-Flanders
- research council of Ghent University
- NSERC
- Sharcnet
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A variational optimization of the second-order density matrix under the P-, Q-, and G-conditions was carried out for a set of diatomic 14-electron molecules, including N-2, O-2(2+), NO+, CO, and CN-. The dissociation of these molecules is studied by analyzing several chemical properties (dipole moments, population analysis, and bond indices) up to the dissociation limit (10 and 20 A degrees). Serious chemical flaws are observed for the heteronuclear diatomics in the dissociation limit. A careful examination of the chemical properties reveals that the origin of the dissociation problem lies in the flawed description of fractionally occupied species under the P-, Q-, and G-conditions. A novel constraint is introduced that imposes the correct dissociation and enforces size consistency. The effect of this constraint is illustrated with calculations on NO+, CO, CN-, N-2, and O-2(2+).
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