Fig. 5: Correlation of angular distortion, from D3h geometry to near C4v geometry as measured by decrease in Θ, and time taken for CO release.
a Schematic representation of degrees of freedom in the angular distortion parameter Θ = Θ1 − Θ2, introduced in Fig. 2a, involving transition from D3h geometry to near C4v geometry; followed by release of CO. The green and orange spheres denote the axial and equatorial ligands which become equivalent upon angular distortion to the nearly C4v geometry. b Scatter plot of the smallest value of Θ, before τdissoc, versus τdissoc for all 110 singly dissociative trajectories. The orange and green solid dots represent release of axial and equatorial CO ligands, respectively. The hollow black dots show the initial distribution of Θ obtained from the Wigner distribution. c The excited singly occupied molecular orbital involved in the the dissociative MC states at ground state D3h geometry (top) and in the near C4v geometry (bottom) which is also the optimized geometry for the S5 state. The pink arrows for both the cases indicate regions of anti-bonding overlap which effectuates the CO dissociation.
