A multireference perturbation method is formulated, that uses an optimized partitioning. The zeroth-order energies are chosen in a way that guarantees vanishing the first neglected term in the perturbational ansatz for the wave function, This procedure yields a family of zeroth-order Hamiltonians that allows for systematic control of errors arising from truncating the perturbative expansion of the wave function. The second-order version of the proposed method, denoted as MROPT(2), is shown to be (almost) size-consistent. The slight extensivity violation is shown numerically. The total energies obtained with MROPT(2) are similar to these obtained using the multireference configuration interaction method with Davidson-type corrections. We discuss connections of the MROPT(2) method to related approaches, the optimized partitioning introduced by Szabados and Surján and the linearized multireference coupled-cluster method. The MROPT(2) method requires using state-optimized orbitals; we show on example of that using Hartree–Fock orbitals for some excited states may lead to nonphysical results.
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8 May 2003
Research Article|
May 08 2003
Multireference perturbation theory with optimized partitioning. I. Theoretical and computational aspects
Henryk A. Witek;
Henryk A. Witek
Department of Applied Chemistry, School of Engineering, The University of Tokyo, Tokyo 113-8656, Japan
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Haruyuki Nakano;
Haruyuki Nakano
Department of Applied Chemistry, School of Engineering, The University of Tokyo, Tokyo 113-8656, Japan
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Kimihiko Hirao
Kimihiko Hirao
Department of Applied Chemistry, School of Engineering, The University of Tokyo, Tokyo 113-8656, Japan
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J. Chem. Phys. 118, 8197–8206 (2003)
Article history
Received:
October 21 2002
Accepted:
February 04 2003
Citation
Henryk A. Witek, Haruyuki Nakano, Kimihiko Hirao; Multireference perturbation theory with optimized partitioning. I. Theoretical and computational aspects. J. Chem. Phys. 8 May 2003; 118 (18): 8197–8206. https://doi.org/10.1063/1.1563618
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