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Multireference Density Functional Theory with Generalized Auxiliary Systems for Ground and Excited States.

Publication ,  Journal Article
Chen, Z; Zhang, D; Jin, Y; Yang, Y; Su, NQ; Yang, W
Published in: The journal of physical chemistry letters
September 2017

To describe static correlation, we develop a new approach to density functional theory (DFT), which uses a generalized auxiliary system that is of a different symmetry, such as particle number or spin, from that of the physical system. The total energy of the physical system consists of two parts: the energy of the auxiliary system, which is determined with a chosen density functional approximation (DFA), and the excitation energy from an approximate linear response theory that restores the symmetry to that of the physical system, thus rigorously leading to a multideterminant description of the physical system. The electron density of the physical system is different from that of the auxiliary system and is uniquely determined from the functional derivative of the total energy with respect to the external potential. Our energy functional is thus an implicit functional of the physical system density, but an explicit functional of the auxiliary system density. We show that the total energy minimum and stationary states, describing the ground and excited states of the physical system, can be obtained by a self-consistent optimization with respect to the explicit variable, the generalized Kohn-Sham noninteracting density matrix. We have developed the generalized optimized effective potential method for the self-consistent optimization. Among options of the auxiliary system and the associated linear response theory, reformulated versions of the particle-particle random phase approximation (pp-RPA) and the spin-flip time-dependent density functional theory (SF-TDDFT) are selected for illustration of principle. Numerical results show that our multireference DFT successfully describes static correlation in bond dissociation and double bond rotation.

Duke Scholars

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Published In

The journal of physical chemistry letters

DOI

EISSN

1948-7185

ISSN

1948-7185

Publication Date

September 2017

Volume

8

Issue

18

Start / End Page

4479 / 4485

Related Subject Headings

  • 51 Physical sciences
  • 34 Chemical sciences
  • 03 Chemical Sciences
  • 02 Physical Sciences
 

Citation

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Chen, Z., Zhang, D., Jin, Y., Yang, Y., Su, N. Q., & Yang, W. (2017). Multireference Density Functional Theory with Generalized Auxiliary Systems for Ground and Excited States. The Journal of Physical Chemistry Letters, 8(18), 4479–4485. https://doi.org/10.1021/acs.jpclett.7b01864
Chen, Zehua, Du Zhang, Ye Jin, Yang Yang, Neil Qiang Su, and Weitao Yang. “Multireference Density Functional Theory with Generalized Auxiliary Systems for Ground and Excited States.The Journal of Physical Chemistry Letters 8, no. 18 (September 2017): 4479–85. https://doi.org/10.1021/acs.jpclett.7b01864.
Chen Z, Zhang D, Jin Y, Yang Y, Su NQ, Yang W. Multireference Density Functional Theory with Generalized Auxiliary Systems for Ground and Excited States. The journal of physical chemistry letters. 2017 Sep;8(18):4479–85.
Chen, Zehua, et al. “Multireference Density Functional Theory with Generalized Auxiliary Systems for Ground and Excited States.The Journal of Physical Chemistry Letters, vol. 8, no. 18, Sept. 2017, pp. 4479–85. Epmc, doi:10.1021/acs.jpclett.7b01864.
Chen Z, Zhang D, Jin Y, Yang Y, Su NQ, Yang W. Multireference Density Functional Theory with Generalized Auxiliary Systems for Ground and Excited States. The journal of physical chemistry letters. 2017 Sep;8(18):4479–4485.
Journal cover image

Published In

The journal of physical chemistry letters

DOI

EISSN

1948-7185

ISSN

1948-7185

Publication Date

September 2017

Volume

8

Issue

18

Start / End Page

4479 / 4485

Related Subject Headings

  • 51 Physical sciences
  • 34 Chemical sciences
  • 03 Chemical Sciences
  • 02 Physical Sciences