Rintelman Jamie M, Adamovic Ivana, Varganov Sergey, Gordon Mark S
Department of Chemistry and Ames Laboratory, US Department of Energy, Iowa State University, Ames, IA 50011, USA.
J Chem Phys. 2005 Jan 22;122(4):44105. doi: 10.1063/1.1817891.
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.
本文对多参考二阶莫勒-普莱塞特微扰理论（MRMP2）方法与尺寸一致性的偏差进行了系统研究。结果表明，尺寸一致性误差取决于超分子计算中单体的数量、基组大小、相关价电子数以及活性空间的大小。以HF、F(2)和N(2)为例，采用拉伸键，以包含简单、明确的多参考特征。这对于确保将MRMP2作为多参考方法进行测试至关重要。研究得出结论，MRMP2和其他多参考微扰理论方法可能会表现出显著的尺寸一致性误差，且误差大小取决于微扰理论的实现方式。
