Physics – Chemical Physics
Scientific paper
2009-10-21
J. Chem. Phys. 132, 114113 (2010)
Physics
Chemical Physics
published version;added references
Scientific paper
10.1063/1.3354911
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.
Aggelen Helen van
Ayers Paul W.
Bultinck Patrick
Neck Dimitri Van
Verstichel Brecht
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