Multireference second-order perturbation theory: How size consistent is "almost size consistent"

被引:77
作者
Rintelman, JM [1 ]
Adamovic, I
Varganov, S
Gordon, MS
机构
[1] Iowa State Univ, Dept Chem, US Dept Energy, Ames, IA 50011 USA
[2] Iowa State Univ, US Dept Energy, Ames Lab, Ames, IA 50011 USA
关键词
D O I
10.1063/1.1817891
中图分类号
O64 [物理化学(理论化学)、化学物理学];
学科分类号
070304 ; 081704 ;
摘要
A systematic study of the deviation from size consistency of the multireference second-order Moller-Plesset perturbation theory (MRMP2) method is presented. The size-consistency error is shown to depend on the number of monomers in a supermolecule calculation, size of basis set, number of correlated valence electrons, and size of active space. HF, F-2, and N-2 are used as test cases, with stretched bonds, to include simple, well-defined multireference character. This is essential in ensuring that MRMP2 is being tested as a multireference method. It is concluded that the MRMP2 and other multireference perturbation theory methods can exhibit significant size-consistency errors, and that the size of the error depends on the manner in which the perturbation theory is implemented. (C) 2005 American Institute of Physics.
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页数:7
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