Chinese Journal of Chemical Physics, Volume. 33, Issue 5, 595(2020)
Photodynamics of Methyl-Vinyl Criegee Intermediate: Different Conical Intersections Govern the Fates of Syn/Anti Configurations†
Fig. 1. The four S
Fig. 1. The active orbitals selected in CAS(14
Fig. 2. Important geometries with key parameters (bond lengths are given in Angstrom) and relative energies (in kcal/mol) calculated at the PBE0/def2-SVP (in black), SA3-CASSCF/def2-SVP (in red), MS3-CASPT2/def2-SVP (in blue) and MS3-CASPT2/def2-TZVP (in green) levels.
Fig. 2. The CASSCF/def2-SVP computed S
Fig. 3. Distributions of the hopping points near the S
Fig. 3. The CASSCF/def2-SVP computed S1-state energy profiles along the C3-C4 rotary coordinate. (a) The isomerization between S1-
Fig. 4. (a) (b) The CASSCF/def2-SVP level 2-D PESs for S1-state photoisomerization (relative energies are shown in kcal/mol). Evolutions of the corresponding (dihedral) angles are shown in (c) and (d), and bond lengths (or distances) are shown in (e) and (f), along the C3-O rotation (dihedral angle
Fig. 4. The major photoisomerization channels of S
Fig. 5. The state population of the S1-state trajectories and excited-state lifetime fitted by a kinetic model.
Fig. 5. Geometrical evolution of trajectories in four configurations of (a) AA, (b) AS, (c) SA and (d) SS, initiated from the S
Fig. 6. Geometry distribution of the first hopping points. The black and green balls show the S1 → S0 and S1 → S2 hops, respectively. For ease of observing, their projections on R-
Fig. 7. Evolution of
Fig. 8. Evolution of dihedral angle
Fig. 9. Quantum populations for an ensemble of all the successful trajectories start from S2 state.
Fig. 10. Geometry and time distribution of all hopping points. The red, blue and black balls show the S2 → S1, S1→S0 and S2 → S1 hops, respectively. For ease of observing, their projections on R(O1-O2)-time and time-
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Ya-zhen Li, Jia-wei Yang, Lily Makroni, Wen-liang Wang, Feng-yi Liu. Photodynamics of Methyl-Vinyl Criegee Intermediate: Different Conical Intersections Govern the Fates of Syn/Anti Configurations†[J]. Chinese Journal of Chemical Physics, 2020, 33(5): 595
Received: Jun. 9, 2020
Accepted: Jul. 23, 2020
Published Online: Apr. 22, 2021
The Author Email: Liu Feng-yi (fengyiliu@snnu.edu.cn)