CaltechAUTHORS
  A Caltech Library Service

Nonadiabatic dynamics with spin-flip vs 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 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

[img] PDF - Submitted Version
Creative Commons Attribution.

6MB

Use this Persistent URL to link to this item: https://resolver.caltech.edu/CaltechAUTHORS:20210720-220452911

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.


Item Type:Article
Related URLs:
URLURL TypeDescription
https://doi.org/10.1063/5.0062757DOIArticle
https://doi.org/10.33774/chemrxiv-2021-gxw1nDOIDiscussion Paper
ORCID:
AuthorORCID
Zhang, Xing0000-0002-1892-1380
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+, 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.
Funders:
Funding AgencyGrant Number
NSFCHE-1300603
NSFCHE-1665322
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

Repository Staff Only: item control page