Communication: Orbital instabilities and triplet states from time-dependent density functional theory and long-range corrected functionals

John S. Sears; Thomas Koerzdoerfer; Cai Rong Zhang; Jean Luc Brédas

doi:10.1063/1.3656734

Communication: Orbital instabilities and triplet states from time-dependent density functional theory and long-range corrected functionals

John S. Sears^*, Thomas Koerzdoerfer, Cai Rong Zhang, Jean Luc Brédas

^*Corresponding author for this work

Research output: Contribution to journal › Article › peer-review

122 Scopus citations

Abstract

Long-range corrected hybrids represent an increasingly popular class of functionals for density functional theory (DFT) that have proven to be very successful for a wide range of chemical applications. In this Communication, we examine the performance of these functionals for time-dependent (TD)DFT descriptions of triplet excited states. Our results reveal that the triplet energies are particularly sensitive to the range-separation parameter; this sensitivity can be traced back to triplet instabilities in the ground state coming from the large effective amounts of Hartree-Fock exchange included in these functionals. As such, the use of standard long-range corrected functionals for the description of triplet states at the TDDFT level is not recommended.

Original language	English (US)
Article number	151103
Journal	JOURNAL OF CHEMICAL PHYSICS
Volume	135
Issue number	15
DOIs	https://doi.org/10.1063/1.3656734
State	Published - Oct 21 2011
Externally published	Yes

Bibliographical note

Funding Information:
This work has been supported by the Air Force Office of Scientific Research through the COMAS MURI Program (Agreement No. FA9550-10-1-0558), by the STC Program (Award No. DMR-0120967), and CRIF Program (Award No. CHE-0946869) of the National Science Foundation. J.S.S. and T.K. gratefully acknowledge Roi Baer, Leeor Kronik, and David Tozer for helpful discussions on time-dependent DFT and long-range corrected functionals. T.K. and C.R.Z. also thank the Alexander-von-Humboldt Foundation and the Chinese Visiting Scholar Program, respectively, for financial support.

ASJC Scopus subject areas

General Physics and Astronomy
Physical and Theoretical Chemistry

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10.1063/1.3656734

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title = "Communication: Orbital instabilities and triplet states from time-dependent density functional theory and long-range corrected functionals",

abstract = "Long-range corrected hybrids represent an increasingly popular class of functionals for density functional theory (DFT) that have proven to be very successful for a wide range of chemical applications. In this Communication, we examine the performance of these functionals for time-dependent (TD)DFT descriptions of triplet excited states. Our results reveal that the triplet energies are particularly sensitive to the range-separation parameter; this sensitivity can be traced back to triplet instabilities in the ground state coming from the large effective amounts of Hartree-Fock exchange included in these functionals. As such, the use of standard long-range corrected functionals for the description of triplet states at the TDDFT level is not recommended.",

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note = "Funding Information: This work has been supported by the Air Force Office of Scientific Research through the COMAS MURI Program (Agreement No. FA9550-10-1-0558), by the STC Program (Award No. DMR-0120967), and CRIF Program (Award No. CHE-0946869) of the National Science Foundation. J.S.S. and T.K. gratefully acknowledge Roi Baer, Leeor Kronik, and David Tozer for helpful discussions on time-dependent DFT and long-range corrected functionals. T.K. and C.R.Z. also thank the Alexander-von-Humboldt Foundation and the Chinese Visiting Scholar Program, respectively, for financial support.",

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AU - Brédas, Jean Luc

N1 - Funding Information: This work has been supported by the Air Force Office of Scientific Research through the COMAS MURI Program (Agreement No. FA9550-10-1-0558), by the STC Program (Award No. DMR-0120967), and CRIF Program (Award No. CHE-0946869) of the National Science Foundation. J.S.S. and T.K. gratefully acknowledge Roi Baer, Leeor Kronik, and David Tozer for helpful discussions on time-dependent DFT and long-range corrected functionals. T.K. and C.R.Z. also thank the Alexander-von-Humboldt Foundation and the Chinese Visiting Scholar Program, respectively, for financial support.

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Communication: Orbital instabilities and triplet states from time-dependent density functional theory and long-range corrected functionals

Abstract

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