Abstract
The purpose of this paper is to introduce a second-order perturbation theory derived from the mathematical framework of the quasiparticle-based multi-reference coupled-cluster approach (Rolik and Kállay in J Chem Phys 141:134112, 2014). The quasiparticles are introduced via a unitary transformation which allows us to represent a complete active space reference function and other elements of an orthonormal multi-reference basis in a determinant-like form. The quasiparticle creation and annihilation operators satisfy the fermion anti-commutation relations. As the consequence of the many-particle nature of the applied unitary transformation these quasiparticles are also many-particle objects, and the Hamilton operator in the quasiparticle basis contains higher than two-body terms. The definition of the new theory strictly follows the form of the single-reference many-body perturbation theory and retains several of its beneficial properties like the extensivity. The efficient implementation of the method is briefly discussed, and test results are also presented.
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Financial support has been provided by the Hungarian Scientific Research Fund (OTKA), Grant No. PD108451.
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Published as part of the special collection of articles “Festschrift in honour of P. R. Surjan”.
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Rolik, Z., Kállay, M. A second-order multi-reference quasiparticle-based perturbation theory. Theor Chem Acc 134, 143 (2015). https://doi.org/10.1007/s00214-015-1746-z
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DOI: https://doi.org/10.1007/s00214-015-1746-z