Spin-restricted ensemble-referenced Kohn-Sham method: basic principles and application to strongly correlated ground and excited states of molecules

被引:128
作者
Filatov, Michael [1 ]
机构
[1] Univ Bonn, Inst Phys & Theoret Chem, Bonn, Germany
关键词
DENSITY-FUNCTIONAL THEORY; POTENTIAL-ENERGY SURFACES; VALENCE-BOND DESCRIPTION; BROKEN-SYMMETRY APPROACH; MANY-PARTICLE SYSTEMS; ELECTRON CORRELATION; TETRAMETHYLENEETHANE TME; CONICAL INTERSECTIONS; EXCITATION-ENERGIES; COUPLING-CONSTANTS;
D O I
10.1002/wcms.1209
中图分类号
O6 [化学];
学科分类号
0703 ;
摘要
Ensemble density functional theory (DFT) is a novel theoretical approach that is capable of exact treatment of non-dynamic electron correlation in the ground and excited states of many-body fermionic systems. In contrast to ordinary DFT, ensemble DFT has not found so far a way to the repertoire of methods of modern computational chemistry, probably owing to the lack of practically affordable implementations of the theory. The spin-restricted ensemble-referenced Kohn-Sham (REKS) method represents perhaps the first computational scheme that makes ensemble DFT calculations feasible. The REKS method is based on the rigorous ensemble representation of the energy and the density of a strongly correlated system and provides for an accurate and consistent description of molecular systems the electronic structure of which is dominated by the non-dynamic correlation. This includes the ground and excited states of molecules undergoing bond breaking/bond formation, the low-spin states of biradicals and polyradicals, symmetry forbidden chemical reactions and avoided crossings of potential energy surfaces, real intersections between the energy surfaces of the ground and excited states (conical intersections), and many more. The REKS method can be employed in connection with any local, semi-local and hybrid (global and range-separated) functional and affords calculations of large and very large molecular systems at a moderate mean-field cost. WIREs Comput Mol Sci 2015, 5:146-167. doi: 10.1002/wcms.1209 Conflict of interest: The author has declared no conflicts of interest for this article. For further resources related to this article, please visit the .
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页码:146 / 167
页数:22
相关论文
共 102 条
[1]   Comment on "About the calculation of exchange coupling constants using density-functional theory: The role of the self-interaction error" [J. Chem. Phys. 123, 164110, 2005] [J].
Adamo, C ;
Barone, V ;
Bencini, A ;
Broer, R ;
Filatov, M ;
Harrison, NM ;
Illas, F ;
Malrieu, JP ;
Moreira, IDR .
JOURNAL OF CHEMICAL PHYSICS, 2006, 124 (10)
[2]   2ND-ORDER PERTURBATION-THEORY WITH A COMPLETE ACTIVE SPACE SELF-CONSISTENT FIELD REFERENCE FUNCTION [J].
ANDERSSON, K ;
MALMQVIST, PA ;
ROOS, BO .
JOURNAL OF CHEMICAL PHYSICS, 1992, 96 (02) :1218-1226
[3]  
Andersson K., 1995, MODERN ELECT STRUCTU, P55, DOI [10.1142/9789812832108_0002, DOI 10.1142/9789812832108_0002]
[4]  
[Anonymous], 2005, J CHEM PHYS
[5]   Excitation energies from time-dependent density-functional formalism for small systems [J].
Aryasetiawan, F ;
Gunnarsson, O ;
Rubio, A .
EUROPHYSICS LETTERS, 2002, 57 (05) :683-689
[6]   POTENTIAL-ENERGY SURFACES NEAR INTERSECTIONS [J].
ATCHITY, GJ ;
XANTHEAS, SS ;
RUEDENBERG, K .
JOURNAL OF CHEMICAL PHYSICS, 1991, 95 (03) :1862-1876
[8]   Why semilocal functionals work: Accuracy of the on-top pair density and importance of system averaging [J].
Burke, K ;
Perdew, JP ;
Ernzerhof, M .
JOURNAL OF CHEMICAL PHYSICS, 1998, 109 (10) :3760-3771
[9]   Remarks on the proper use of the broken symmetry approach to magnetic coupling [J].
Caballol, R ;
Castell, O ;
Illas, F ;
Moreira, PR ;
Malrieu, JP .
JOURNAL OF PHYSICAL CHEMISTRY A, 1997, 101 (42) :7860-7866
[10]  
Casida ME, 2012, ANNU REV PHYS CHEM, V63, P287, DOI [10.1146/annurev-physchem-032511-143803, 10.1146/annurev-physchem-032511-443803]