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Efficient implementations of analytic energy gradient for mixed-reference spin-flip time-dependent density functional theory (MRSF-TDDFT)
Cited 35 time in
Web of Science
Cited 36 time in Scopus
- Authors
- Issue Date
- 2019-05
- Publisher
- American Institute of Physics
- Citation
- Journal of Chemical Physics, Vol.150 No.18, p. 184111
- Abstract
- Analytic energy gradients of individual singlet and triplet states with respect to nuclear coordinates are derived and implemented for the collinear mixed-reference spin-flip time-dependent density functional theory (MRSF-TDDFT), which eliminates the problematic spin-contamination of SF-TDDFT. Dimensional-transformation matrices for the singlet and triplet response spaces are introduced, simplifying the subsequent derivations. These matrices enable the general forms of MRSF-TDDFT equations to be similar to those of SF-TDDFT, suggesting that the computational overhead of singlet or triplet states for MRSF-TDDFT is nearly identical to that of SF-TDDFT. In test calculations, the new MRSF-TDDFT yields quite different optimized structures and energies as compared to SF-TDDFT. These differences turned out to mainly come from the spin-contamination of SF-TDDFT, which are largely cured by MRSF-TDDFT. In addition, it was demonstrated that the clear separation of singlet states from triplets dramatically simplifies the location of minimum energy conical intersection. As a result, it is clear that the MRSF-TDDFT has advantages over SF-TDDFT in terms of both accuracy and practicality. Therefore, it can be a preferred method, which is readily applied to other black-box type applications, such as the minimum-energy optimization, reaction path following, and molecular dynamics simulations.
- ISSN
- 0021-9606
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