Variational second order density matrix study of F3−: Importance of subspace constraints for size-consistency

H. van Aggelen, B. Verstichel, P. Bultinck, D. Van Neck, P.W. Ayers, D.L. Cooper
Journal of Chemical Physics
134, 054115


Variational second order density matrix theory under “two-positivity” constraints tends to dissociate molecules into unphysical fractionally charged products with too low energies. We aim to construct a qualitatively correct potential energy surface for F3− by applying subspace energy constraints on mono- and diatomic subspaces of the molecular basis space. Monoatomic subspace constraints do not guarantee correct dissociation: the constraints are thus geometry dependent. Furthermore, the number of subspace constraints needed for correct dissociation does not grow linearly with the number of atoms. The subspace constraints do impose correct chemical properties in the dissociation limit and size-consistency, but the structure of the resulting second order density matrix method does not exactly correspond to a system of noninteracting units. © 2011 American Institute of Physics

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