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Multipartitioning Møller–Plesset perturbation theory: Size‐extensivity at third order and symmetry conservation
Author(s) -
Rolik Zoltán,
Szabados Ágnes
Publication year - 2009
Publication title -
international journal of quantum chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.484
H-Index - 105
eISSN - 1097-461X
pISSN - 0020-7608
DOI - 10.1002/qua.22059
Subject(s) - hamiltonian (control theory) , physics , quantum mechanics , møller–plesset perturbation theory , perturbation theory (quantum mechanics) , third order , quantum , explicit symmetry breaking , symmetry (geometry) , mathematical physics , symmetry breaking , theoretical physics , spontaneous symmetry breaking , mathematics , geometry , mathematical optimization , philosophy , theology
Multipartitioning multireference many‐body perturbation theory (Zaitevskii and Malrieu, Chem. Phys. Lett. 1995, 233, 597) is investigated with regard to symmetry and size‐extensivity. We show that the spin‐adapted formulation suffers from spatial symmetry breaking and propose a general symmetry‐conserving zero‐order Hamiltonian. We analyze size‐extensivity of various partitionings at the third order and find that extensivity holds if one‐particle quantities in the zero‐order Hamiltonian are properly chosen. In particular, third order of the spin‐adapted and general symmetry‐adapted theory prove to be extensive. © 2009 Wiley Periodicals, Inc. Int J Quantum Chem, 2009