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Chemical verification of variational second-order density matrix based potential energy surfaces for the N-2 isoelectronic series

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HPC-UGent: the central High Performance Computing infrastructure of Ghent University
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 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+).
Keywords
dissociation energies, carbon compounds, molecular moments, negative ions, nitrogen, nitrogen compounds, positive ions, oxygen, variational techniques, potential energy surfaces, FUNCTIONAL THEORY, BOND ORDER, VALENCE, SYSTEMS

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Citation

Please use this url to cite or link to this publication:

Chicago
van Aggelen, Helen, Brecht Verstichel, Patrick Bultinck, Dimitri Van Neck, Paul W Ayers, and David L Cooper. 2010. “Chemical Verification of Variational Second-order Density Matrix Based Potential Energy Surfaces for the N-2 Isoelectronic Series.” Journal of Chemical Physics 132 (11).
APA
van Aggelen, H., Verstichel, B., Bultinck, P., Van Neck, D., Ayers, P. W., & Cooper, D. L. (2010). Chemical verification of variational second-order density matrix based potential energy surfaces for the N-2 isoelectronic series. JOURNAL OF CHEMICAL PHYSICS, 132(11).
Vancouver
1.
van Aggelen H, Verstichel B, Bultinck P, Van Neck D, Ayers PW, Cooper DL. Chemical verification of variational second-order density matrix based potential energy surfaces for the N-2 isoelectronic series. JOURNAL OF CHEMICAL PHYSICS. 2010;132(11).
MLA
van Aggelen, Helen et al. “Chemical Verification of Variational Second-order Density Matrix Based Potential Energy Surfaces for the N-2 Isoelectronic Series.” JOURNAL OF CHEMICAL PHYSICS 132.11 (2010): n. pag. Print.
@article{701157,
  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 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+).},
  articleno    = {114112},
  author       = {van Aggelen, Helen and Verstichel, Brecht and Bultinck, Patrick and Van Neck, Dimitri and Ayers, Paul W and Cooper, David L},
  issn         = {0021-9606},
  journal      = {JOURNAL OF CHEMICAL PHYSICS},
  keywords     = {dissociation energies,carbon compounds,molecular moments,negative ions,nitrogen,nitrogen compounds,positive ions,oxygen,variational techniques,potential energy surfaces,FUNCTIONAL THEORY,BOND ORDER,VALENCE,SYSTEMS},
  language     = {eng},
  number       = {11},
  pages        = {10},
  title        = {Chemical verification of variational second-order density matrix based potential energy surfaces for the N-2 isoelectronic series},
  url          = {http://dx.doi.org/10.1063/1.3354910},
  volume       = {132},
  year         = {2010},
}

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