Benzenium-Ethene Complex: A Fundamental Problem for Standard Second-Order Moller-Plesset Theory

被引：19

作者：

Schwabe, Tobias ^{[1
]}

Grimme, Stefan ^{[1
]}

机构：

[1] Univ Munster, Inst Organ Chem, D-48149 Munster, Germany

来源：

JOURNAL OF PHYSICAL CHEMISTRY A | 2009年 / 113卷 / 13期

关键词：

AUXILIARY BASIS-SETS; ETHENE/BENZENIUM ION COMPLEX; GAUSSIAN-BASIS SETS; ATOMS; MP2; RI-MP2; CONVERGENCE; MOLECULES; ACCURACY; VALENCE;

D O I：

10.1021/jp9003938

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：

Recently, Kolboe and Svelle pointed out that second-order Moller-Plesset perturbation theory (MP2) incorrectly predicts a barrierless reaction of the benzenium-ethene complex to the ethyl-1H-benzene cation in contrast to other considered quantum chemical methods [J. Phys. Chem. A 2008, 112, 6399]. In a subsequent Letter in this Journal, van Mourik related this behavior to the basis set superposition error [J. Phys. Chem. A 2008, 112, 11017]. Here we call show that this is not the case but that the failure is due to an intrinsic (overcorrelation) problem of MP2. Improved perturbation methods (SCS-MP2 and B2PLYP double-hybrid functionals) provide correct results.

引用

页码：3005 / 3008

页数：4

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