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      Subsystem constraints in variational second order density matrix optimization: curing the dissociative behavior

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          Abstract

          A previous study of diatomic molecules revealed that variational second-order density matrix theory has serious problems in the dissociation limit when the N-representability is imposed at the level of the usual two-index (P, Q, G) or even three-index (T1, T2) conditions [H. van Aggelen et al., Phys. Chem. Chem. Phys. 11, 5558 (2009)]. Heteronuclear molecules tend to dissociate into fractionally charged atoms. In this paper we introduce a general class of N-representability conditions, called subsystem constraints, and show that they cure the dissociation problem at little additional computational cost. As a numerical example the singlet potential energy surface of BeB+ is studied. The extension to polyatomic molecules, where more subsystem choices can be identified, is also discussed.

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          Most cited references17

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          Quantum Theory of Many-Particle Systems. I. Physical Interpretations by Means of Density Matrices, Natural Spin-Orbitals, and Convergence Problems in the Method of Configurational Interaction

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            Structure of Fermion Density Matrices

            A. Coleman (1963)
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              Reduction of the N‐Particle Variational Problem

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                Author and article information

                Journal
                21 October 2009
                2010-03-18
                Article
                10.1063/1.3354911
                0910.4094
                6c5d40c8-5ad7-4268-8baf-70326294c61a

                http://arxiv.org/licenses/nonexclusive-distrib/1.0/

                History
                Custom metadata
                J. Chem. Phys. 132, 114113 (2010)
                published version;added references
                physics.chem-ph

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