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Nonadiabatic dynamics with spin-flip versus linear-response time-dependent density functional theory: A case study for the protonated Schiff base C₅H₆NH₂⁺

Zhang, Xing and Herbert, John (2021) Nonadiabatic dynamics with spin-flip versus linear-response time-dependent density functional theory: A case study for the protonated Schiff base C₅H₆NH₂⁺. . (Unpublished) https://resolver.caltech.edu/CaltechAUTHORS:20210720-220452911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 is able to correctly describe 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.


Item Type:Report or Paper (Discussion Paper)
Related URLs:
URLURL TypeDescription
https://doi.org/10.33774/chemrxiv-2021-gxw1nDOIDiscussion Paper
ORCID:
AuthorORCID
Herbert, John0000-0002-1663-2278
Alternate Title:Nonadiabatic dynamics with spin-flip versus linear-response time-dependent density functional theory: A case study for the protonated Schiff base C5H6NH2+
Additional Information:The content is available under CC BY 4.0 License. Jul 08, 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). J.M.H. serves on the board of directors of Q-Chem Inc. Data availability statement: The data that support the findings of this study are available from the corresponding author upon reasonable request. Author’s competing interest statement: J.M.H. serves on the board of directors of Q-Chem Inc. Ethics: The author(s) declare that they have sought and gained approval from the relevant ethics committee/IRB for this research and its publication.
Funders:
Funding AgencyGrant Number
NSFCHE-1300603
NSFCHE-1665322
Subject Keywords:conical intersection; time-dependent density functional theory; surface hopping
Record Number:CaltechAUTHORS:20210720-220452911
Persistent URL:https://resolver.caltech.edu/CaltechAUTHORS:20210720-220452911
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:21 Jul 2021 16:18

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