哈特里-福克轨道显著提高了由半局域密度泛函预测的反应势垒高度。
Hartree-Fock orbitals significantly improve the reaction barrier heights predicted by semilocal density functionals.
作者信息
Janesko Benjamin G, Scuseria Gustavo E
机构信息
Department of Chemistry, Rice University, Houston, Texas 77005, USA.
出版信息
J Chem Phys. 2008 Jun 28;128(24):244112. doi: 10.1063/1.2940738.
Abstract
Semilocal density functional theory predictions for the barrier heights of representative hydrogen transfer, heavy-atom transfer, and nucleophilic substitution reactions are significantly improved in non-self-consistent calculations using Hartree-Fock orbitals. Orbitals from hybrid calculations yield related improvements. These results provide insight into compensating for one-electron self-interaction error in semilocal density functional theory.
摘要
在使用哈特里-福克轨道的非自洽计算中，半局域密度泛函理论对代表性氢转移、重原子转移和亲核取代反应势垒高度的预测有显著改善。混合计算得到的轨道也有相关改进。这些结果为补偿半局域密度泛函理论中的单电子自相互作用误差提供了见解。
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1
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J Chem Phys. 2007 Dec 14;127(22):221103. doi: 10.1063/1.2822021.
2
Tests of functionals for systems with fractional electron number.具有分数电子数的系统的泛函测试。
J Chem Phys. 2007 Apr 21;126(15):154109. doi: 10.1063/1.2723119.
3
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J Chem Phys. 2006 Dec 21;125(23):234109. doi: 10.1063/1.2409292.
4
Many-electron self-interaction error in approximate density functionals.近似密度泛函中的多电子自相互作用误差
J Chem Phys. 2006 Nov 28;125(20):201102. doi: 10.1063/1.2403848.
5
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J Chem Phys. 2006 Nov 21;125(19):194112. doi: 10.1063/1.2387954.
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J Chem Phys. 2006 Mar 7;124(9):94108. doi: 10.1063/1.2176608.
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