MISC

2003年5月

Multireference perturbation theory with optimized partitioning. I. Theoretical and computational aspects

JOURNAL OF CHEMICAL PHYSICS
  • HA Witek
  • ,
  • H Nakano
  • ,
  • K Hirao

118
18
開始ページ
8197
終了ページ
8206
記述言語
英語
掲載種別
DOI
10.1063/1.1563618
出版者・発行元
AMER INST PHYSICS

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, Psi((n))=0. 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 Surjan and the linearized multireference coupled-cluster method. The MROPT(2) method requires using state-optimized orbitals; we show on example of N-2 that using Hartree-Fock orbitals for some excited states may lead to nonphysical results. (C) 2003 American Institute of Physics.

リンク情報
DOI
https://doi.org/10.1063/1.1563618
Web of Science
https://gateway.webofknowledge.com/gateway/Gateway.cgi?GWVersion=2&SrcAuth=JSTA_CEL&SrcApp=J_Gate_JST&DestLinkType=FullRecord&KeyUT=WOS:000182454100009&DestApp=WOS_CPL
ID情報
  • DOI : 10.1063/1.1563618
  • ISSN : 0021-9606
  • eISSN : 1089-7690
  • Web of Science ID : WOS:000182454100009

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