In this paper, a hybrid density functional valence bond method based on unpaired electron density, called λ-DFVB(U), is presented, which is a combination of the valence bond self-consistent field (VBSCF) method and Kohn–Sham density functional theory. In λ-DFVB(U), the double-counting error of electron correlation is mitigated by a linear decomposition of the electron–electron interaction using a parameter λ, which is a function of an index based on the number of effectively unpaired electrons. In addition, λ-DFVB(U) is based on the approximation that correlation functionals in KS-DFT only cover dynamic correlation and exchange functionals mimic some amount of static correlation. Furthermore, effective spin densities constructed from unpaired density are used to address the symmetry dilemma problem in λ-DFVB(U). The method is applied to test calculations of atomization energies, atomic excitation energies, and reaction barriers. It is shown that the accuracy of λ-DFVB(U) is comparable to that of CASPT2, while its computational cost is approximately the same as VBSCF.
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28 May 2022
Research Article|
May 23 2022
λ-DFVB(U): A hybrid density functional valence bond method based on unpaired electron density
Special Collection:
Nature of the Chemical Bond
Peikun Zheng
;
Peikun Zheng
State Key Laboratory of Physical Chemistry of Solid Surfaces, Fujian Provincial Key Laboratory of Theoretical and Computational Chemistry, Department of Chemistry, and College of Chemistry and Chemical Engineering, Xiamen University
, Xiamen 361005, China
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Zixi Gan;
Zixi Gan
State Key Laboratory of Physical Chemistry of Solid Surfaces, Fujian Provincial Key Laboratory of Theoretical and Computational Chemistry, Department of Chemistry, and College of Chemistry and Chemical Engineering, Xiamen University
, Xiamen 361005, China
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Chen Zhou
;
Chen Zhou
a)
State Key Laboratory of Physical Chemistry of Solid Surfaces, Fujian Provincial Key Laboratory of Theoretical and Computational Chemistry, Department of Chemistry, and College of Chemistry and Chemical Engineering, Xiamen University
, Xiamen 361005, China
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Peifeng Su
;
Peifeng Su
State Key Laboratory of Physical Chemistry of Solid Surfaces, Fujian Provincial Key Laboratory of Theoretical and Computational Chemistry, Department of Chemistry, and College of Chemistry and Chemical Engineering, Xiamen University
, Xiamen 361005, China
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Wei Wu
Wei Wu
a)
State Key Laboratory of Physical Chemistry of Solid Surfaces, Fujian Provincial Key Laboratory of Theoretical and Computational Chemistry, Department of Chemistry, and College of Chemistry and Chemical Engineering, Xiamen University
, Xiamen 361005, China
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Peikun Zheng
Zixi Gan
Chen Zhou
a)
Peifeng Su
Wei Wu
a)
State Key Laboratory of Physical Chemistry of Solid Surfaces, Fujian Provincial Key Laboratory of Theoretical and Computational Chemistry, Department of Chemistry, and College of Chemistry and Chemical Engineering, Xiamen University
, Xiamen 361005, China
Note: This paper is part of the JCP Special Topic on Nature of the Chemical Bond.
J. Chem. Phys. 156, 204103 (2022)
Article history
Received:
March 16 2022
Accepted:
May 02 2022
Citation
Peikun Zheng, Zixi Gan, Chen Zhou, Peifeng Su, Wei Wu; λ-DFVB(U): A hybrid density functional valence bond method based on unpaired electron density. J. Chem. Phys. 28 May 2022; 156 (20): 204103. https://doi.org/10.1063/5.0091592
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