FGR-type decay from min: time evolution of the ground-state population.
HOMO evolution along three different pathways on the and surfaces. Panel a: interpolated pathway from min to a X point similar to that reported in Ref. 14. Panel b: MEP connecting , and through the seam. Panel c: portion of the seam of CoIn reported in Ref. 12. Two different views of the same orbital are given.
The , , and potential energy surfaces sketched along reaction coordinates leading either to radical (red) or molecular (green or black) dissociation. The CAS(10,9) energies of the main stationary points are given in kcal/mol. The only intersection shown here (red curves) corresponds to the low-energy degenerate asymptote of the radical products.
energies (dashed red line) and energies (solid black line) at seam geometries. CAS(10,9) energies are given against min.
The (solid red line) and seams of intersection. Two different regions of the seam can be distinguished (pair of dashed green lines and dotted black line) depending on the value of the most extended CH bond length. Panel a: geometry of the points represented by the HCH angle against the most extended CH bond length. Panel b: energy of the points plotted against the most extended CH bond length. CAS(10,9) energies are given against min. The black cross denotes the MSX point from Ref. 14 (recalculated with the same level as our other points).
Trajectories and pathways in leading to two different regions of the seam represented in the plane of the HCH angle and the most extended CH bond length. Black square: min; black triangle: TS; black crosses: crossings; dashed pink line: MEP connecting to the seam (via TS); solid blue line: dynamics trajectory with no extra momentum, connecting TS to the seam; dotted orange line: dynamics trajectory with some extra momentum connecting a point near to TS to the seam; and long dash-dotted green line: minimization of the energy difference starting from TS.
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