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 journalArticlepeer-review

118 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 languageEnglish (US)
Article number151103
JournalJOURNAL OF CHEMICAL PHYSICS
Volume135
Issue number15
DOIs
StatePublished - Oct 21 2011
Externally publishedYes

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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