Stationary and intersection structures on the isomerization pathways between 4-methyloyridine and prefulvene, along with the atom-labeling scheme illustrated in the 4MPy(S0) structure and the key bond distances (Å) for 4MPy (S2), TS(S2), S2/S0_PF, PF(S0), and PF_TS_BV(S0) at the CAS(8,7)/6–31G* level and for 4MPy(S0), BV(S0), BV_TS_3MPy(S0), BV_TS_4MPy(S0), and 3MPy(S0) at the B3LYP/6–311G** level.
Stationary and intersection structures and their relative energies for the isomerization between 4-methylpyridine and Dewar isomer. (a) Stationary and intersection structures along with the key bond distances (Å) for 4MPy (S2) and S2/S0_M at the CAS(8,7)/6–31G* level and for M(S0), M_TS_D1(S0), D1_TS_4MPy(S0), and 4MPy(S0) at the B3LYP/6–311G** level. (b) The relative energies (in kcal/mol).
Schematic potential energy profiles for the isomerization to prefulvene and subsequent processes, along with the relative energies (in kcal/mol) calculated at the CASPT2 level without zero-point energy correction (a) and calculated at the B3LYP/6–311G** level with zero-point energy correction (b).
Potential energies of the populated states are plotted as a function of time for 89 trajectories starting from the TS(S2) structure.
Time evolution of energies (a), the C2–C6 distance (b), and the N1–C3 distance (c) for the four reactive trajectories.
The key distances are plotted as a function of time for five trajectories, (a) and (b) with the BV_TS_4MPy(S0) geometry as the initial point, (c) and (d) with the BV_TS_3MPy(S0) geometry as the initial point.
(a) Potential energies of the S0 state plotted as a function of time for 50 trajectories starting from the S2/S0_M structure, (b) time evolution of the C2–C4–C6–C5 dihedral angle for four reactive trajectories to Mobius form.
The C3–C6 distance (Å) is plotted as a function of for five trajectories, (a) and (b) with the M_TS_D1(S0) geometry as the initial point, (c) and (d) with the D1_TS_4MPy(S0) geometry as the initial point.
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