Zhang, Xing and Herbert, John (2021) Nonadiabatic dynamics with spin-flip vs linear-response time-dependent density functional theory: A case study for the protonated Schiff base C₅H₆NH₂⁺. Journal of Chemical Physics, 155 (12). Art. No. 124111. ISSN 0021-9606. doi:10.1063/5.0062757. https://resolver.caltech.edu/CaltechAUTHORS:20210720-220452911
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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.
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| Alternate Title: | Nonadiabatic dynamics with spin-flip versus linear-response time-dependent density functional theory: A case study for the protonated Schiff base C5H6NH2+, Nonadiabatic dynamics with spin-flip versus linear-response time-dependent density functional theory: A case study for the protonated Schiff base C₅H₆NH₂⁺ | |||||||||
| 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. | |||||||||
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| Issue or Number: | 12 | |||||||||
| DOI: | 10.1063/5.0062757 | |||||||||
| Record Number: | CaltechAUTHORS:20210720-220452911 | |||||||||
| Persistent URL: | https://resolver.caltech.edu/CaltechAUTHORS:20210720-220452911 | |||||||||
| Official Citation: | Xing Zhang and John M. Herbert , "Nonadiabatic dynamics with spin-flip vs linear-response time-dependent density functional theory: A case study for the protonated Schiff base C₅H₆NH₂⁺, J. Chem. Phys. 155, 124111 (2021) https://doi.org/10.1063/5.0062757 | |||||||||
| Usage Policy: | No commercial reproduction, distribution, display or performance rights in this work are provided. | |||||||||
| ID Code: | 109941 | |||||||||
| Collection: | CaltechAUTHORS | |||||||||
| Deposited By: | Tony Diaz | |||||||||
| Deposited On: | 21 Jul 2021 16:18 | |||||||||
| Last Modified: | 05 Oct 2021 20:22 |
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