Nonadiabatic Dynamics of 1,3-Cyclohexadiene by Curvature-Driven Coherent Switching with Decay of Mixing

Linyao Zhang, Yinan Shu, Suman Bhaumik, Xiye Chen, Shaozeng Sun, Yudong Huang, Donald G. Truhlar

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3 Scopus citations


The photoinduced ring-opening reaction of 1,3-cyclohexadiene to produce 1,3,5-hexatriene is a classic electrocyclic reaction and is also a prototype for many reactions of biological and synthetic importance. Here, we simulate the ultrafast nonadiabatic dynamics of the reaction in the manifold of the three lowest valence electronic states by using extended multistate complete-active-space second-order perturbation theory (XMS-CASPT2) combined with the curvature-driven coherent switching with decay of mixing (κCSDM) dynamical method. We obtain an excited-state lifetime of 79 fs, and a product quantum yield of 40% from the 500 trajectories initiated in the S1excited state. The obtained lifetime and quantum yield values are very close to previously reported experimental and computed values, showing the capability of performing a reasonable nonadiabatic ring-opening dynamics with the κCSDM method that does not require nonadiabatic coupling vectors, time derivatives, or diabatization. In addition, we study the ring-opening reaction by initiating the trajectories in the dark state S2. We also optimize the S0/S1and S1/S2minimum-energy conical intersections (MECIs) by XMS-CASPT2; for S1/S2, we optimized both an inner and an outer local-minimum-energy conical intersections (LMECIs). We provide the potential energy profile along the ring-opening coordinate by joining selected critical points via linear synchronous transit paths. We find the inner S1/S2LMECI to be more crucial than the outer one.

Original languageEnglish (US)
Pages (from-to)7073-7081
Number of pages9
JournalJournal of Chemical Theory and Computation
Issue number12
StatePublished - Dec 13 2022

Bibliographical note

Funding Information:
This work was supported in part by the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences under award DE-SC0015997 and the China Postdoctoral Science Foundation (2022M710032).

Publisher Copyright:
© 2022 American Chemical Society. All rights reserved.

PubMed: MeSH publication types

  • Journal Article


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