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J Phys Chem Lett. 2017 Oct 5;8(19):4838-4845. doi: 10.1021/acs.jpclett.7b02202. Epub 2017 Sep 22.

Spin-Multiplet Components and Energy Splittings by Multistate Density Functional Theory.

Grofe A1,2, Chen X1,2, Liu W3, Gao J1,2.

Author information

1
Theoretical Chemistry Institute, Jilin University , Changchun, Jilin Province 130023, People's Republic of China.
2
Department of Chemistry, University of Minnesota , Minneapolis, Minnesota 55455, United States.
3
Beijing National Laboratory for Molecular Sciences and College of Chemistry and Molecular Engineering , Beijing 100871, People's Republic of China.

Abstract

Kohn-Sham density functional theory has been tremendously successful in chemistry and physics. Yet, it is unable to describe the energy degeneracy of spin-multiplet components with any approximate functional. This work features two contributions. (1) We present a multistate density functional theory (MSDFT) to represent spin-multiplet components and to determine multiplet energies. MSDFT is a hybrid approach, taking advantage of both wave function theory and density functional theory. Thus, the wave functions, electron densities and energy density-functionals for ground and excited states and for different components are treated on the same footing. The method is illustrated on valence excitations of atoms and molecules. (2) Importantly, a key result is that for cases in which the high-spin components can be determined separately by Kohn-Sham density functional theory, the transition density functional in MSDFT (which describes electronic coupling) can be defined rigorously. The numerical results may be explored to design and optimize transition density functionals for configuration coupling in multiconfigurational DFT.

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