Nonadiabatic dynamics with spin-flip vs linear-response time-dependent density functional theory: A case study for the protonated Schiff base C₅H₆NH₂⁺
- Creators
- Zhang, Xing
- Herbert, John
Abstract
Nonadiabatic trajectory surface hopping simulations are reported for trans- C₅H₆NH₂⁺, a model of the rhodopsin chromophore, using the augmented fewest-switches algorithm. Electronic structure calculations were performed using time-dependent density functional theory (TDDFT) in both its conventional linear-response (LR) and its spin-flip (SF) formulations. In the SF-TDDFT case, spin contamination in the low-lying singlet states is removed by projecting out the lowest triplet component during iterative solution of the TDDFT eigenvalue problem. The results show that SF-TDDFT qualitatively describes the photoisomerization of trans- C₅H₆NH₂⁺, with favorable comparison to previous studies using multireference electronic structure methods. In contrast, conventional LR-TDDFT affords qualitatively different photodynamics due to an incorrect excited-state potential surface near the Franck–Condon region. In addition, the photochemistry (involving pre-twisting of the central double bond) appears to be different for SF- and LR-TDDFT, which may be a consequence of different conical intersection topographies afforded by these two methods. The present results contrast with previous surface-hopping studies suggesting that the LR-TDDFT method's incorrect topology around S₁/S₀ conical intersections is immaterial to the photodynamics.
Additional Information
© 2021 Author(s). Published under an exclusive license by AIP Publishing. Submitted: 8 July 2021; Accepted: 9 September 2021; Published Online: 28 September 2021. This work was supported by the National Science Foundation (Grant Nos. CHE-1300603 and CHE-1665322), and calculations were performed at the Ohio Supercomputer Center (Project No. PAA-0003).69 J.M.H. serves on the board of directors of Q-Chem, Inc. Data Availability: The data that support the findings of this study are available from the corresponding author upon reasonable request.Attached Files
Published - 124111_1_online.pdf
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Additional details
- Alternative title
- Nonadiabatic dynamics with spin-flip versus linear-response time-dependent density functional theory: A case study for the protonated Schiff base C5H6NH2+
- Alternative title
- Case study for the protonated Schiff base C₅H₆NH₂⁺
- Eprint ID
- 109941
- Resolver ID
- CaltechAUTHORS:20210720-220452911
- CHE-1300603
- NSF
- CHE-1665322
- NSF
- Created
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2021-07-21Created from EPrint's datestamp field
- Updated
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2023-10-03Created from EPrint's last_modified field