PMID- 36350795
OWN - NLM
STAT- PubMed-not-MEDLINE
DCOM- 20221213
LR  - 20221221
IS  - 1549-9626 (Electronic)
IS  - 1549-9618 (Linking)
VI  - 18
IP  - 12
DP  - 2022 Dec 13
TI  - Nonadiabatic Dynamics of 1,3-Cyclohexadiene by Curvature-Driven Coherent 
      Switching with Decay of Mixing.
PG  - 7073-7081
LID - 10.1021/acs.jctc.2c00801 [doi]
AB  - 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 (kappaCSDM) 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 S(1) excited 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 kappaCSDM 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 S(2). We also optimize the S(0)/S(1) and S(1)/S(2) minimum-energy 
      conical intersections (MECIs) by XMS-CASPT2; for S(1)/S(2), 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 
      S(1)/S(2) LMECI to be more crucial than the outer one.
FAU - Zhang, Linyao
AU  - Zhang L
AUID- ORCID: 0000-0003-1848-8860
AD  - School of Energy Science and Engineering, Harbin Institute of Technology, Harbin 
      150001, P. R. China.
AD  - School of Chemistry and Chemical Engineering, Harbin Institute of Technology, 
      Harbin 150001, P. R. China.
FAU - Shu, Yinan
AU  - Shu Y
AUID- ORCID: 0000-0002-8371-0221
AD  - Department of Chemistry and Supercomputing Institute, University of Minnesota, 
      Minneapolis, Minnesota 55455-0431, United States.
FAU - Bhaumik, Suman
AU  - Bhaumik S
AUID- ORCID: 0000-0002-9568-0656
AD  - Department of Chemistry and Supercomputing Institute, University of Minnesota, 
      Minneapolis, Minnesota 55455-0431, United States.
FAU - Chen, Xiye
AU  - Chen X
AUID- ORCID: 0000-0003-3688-8032
AD  - School of Energy Science and Engineering, Harbin Institute of Technology, Harbin 
      150001, P. R. China.
AD  - School of Chemistry and Chemical Engineering, Harbin Institute of Technology, 
      Harbin 150001, P. R. China.
FAU - Sun, Shaozeng
AU  - Sun S
AUID- ORCID: 0000-0003-2793-5925
AD  - School of Energy Science and Engineering, Harbin Institute of Technology, Harbin 
      150001, P. R. China.
FAU - Huang, Yudong
AU  - Huang Y
AD  - School of Chemistry and Chemical Engineering, Harbin Institute of Technology, 
      Harbin 150001, P. R. China.
FAU - Truhlar, Donald G
AU  - Truhlar DG
AUID- ORCID: 0000-0002-7742-7294
AD  - Department of Chemistry and Supercomputing Institute, University of Minnesota, 
      Minneapolis, Minnesota 55455-0431, United States.
LA  - eng
PT  - Journal Article
DEP - 20221109
PL  - United States
TA  - J Chem Theory Comput
JT  - Journal of chemical theory and computation
JID - 101232704
SB  - IM
EDAT- 2022/11/10 06:00
MHDA- 2022/11/10 06:01
CRDT- 2022/11/09 13:23
PHST- 2022/11/10 06:00 [pubmed]
PHST- 2022/11/10 06:01 [medline]
PHST- 2022/11/09 13:23 [entrez]
AID - 10.1021/acs.jctc.2c00801 [doi]
PST - ppublish
SO  - J Chem Theory Comput. 2022 Dec 13;18(12):7073-7081. doi: 
      10.1021/acs.jctc.2c00801. Epub 2022 Nov 9.