Mixed-Reference Spin-Flip Time-Dependent Density Functional Theory: Multireference Advantages with the Practicality of Linear Response Theory
Abstract
The density functional theory (DFT) and linear response (LR) time-dependent (TD)-DFT are of the utmost importance for routine computations. However, the single reference formulation of DFT suffers in the description of open-shell singlet systems such as diradicals and bond-breaking. LR-TDDFT, on the other hand, finds difficulties in the modeling of conical intersections, doubly excited states, and core-level excitations. In this Perspective, we demonstrate that many of these limitations can be overcome by recently developed mixed-reference (MR) spin-flip (SF)-TDDFT, providing an alternative yet accurate route for such challenging situations. Empowered by the practicality of the LR formalism, it is anticipated that MRSF-TDDFT can become one of the major workhorses for general routine tasks.
Copyright and License
© 2022 The Authors. Published by American Chemical Society. This publication is licensed under CC-BY-NC-ND 4.0.
Acknowledgement
We are indebted to Prof. Klaus Ruedenberg, Prof. Mark Gordon, Dr. Mike Schmidt, Dr. Micheal Filatov, Dr. Miquel Huix-Rotllant, Dr. Hiroya Nakata, Prof. Piotr Piecuch, and Prof. Tao Tzeng for invaluable discussions and inspirations. This work was supported by the NRF funded by the Ministry of Science and ICT (2020R1A2C2008246 and 2020R1A5A1019141 to C.H.C.) for the applications of developed theories. This work was supported by the National Supercomputing Center with supercomputing resources including technical support (KSC-2022-CRE-0353).
Conflict of Interest
The authors declare no competing financial interest.
Files
jz3c02296.pdf
Files
(9.6 MB)
| Name | Size | Download all |
|---|---|---|
|
md5:462eebb9c09299673519410d79cb417a
|
6.5 MB | Preview Download |
|
md5:649466f17ec23766c440418a61baf706
|
3.2 MB | Preview Download |
Additional details
Identifiers
- ISSN
- 1948-7185
- PMCID
- PMC10561896
Related works
- Is supplemented by
- https://pubs.acs.org/doi/suppl/10.1021/acs.jpclett.3c02296/suppl_file/jz3c02296_si_001.pdf (URL)
Funding
- National Research Foundation of Korea
- 2020R1A2C2008246
- National Research Foundation of Korea
- 2020R1A5A1019141
- National Supercomputing Center, Korea Institute of Science and Technology Information
- KSC-2022-CRE-0353