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Chemical verification of variational second-order density matrix based potential energy surfaces for the N2
Helen van Aggelen1, Brecht Verstichel, Patrick Bultinck
1Department of Inorganic and Physical Chemistry, Ghent University, Krijgslaan 281 S3, 9000 Ghent, Belgium.
Abstract:
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). 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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