Photodissociation Dynamics of CH₂OO on Multiple Potential Energy Surfaces: Experiment and Theory

UV excitation of the CH₂OO Criegee intermediate across most of the broad span of the (B ¹A')-(X ¹A') spectrum results in prompt dissociation to two energetically accessible asymptotes: O (¹D) + H₂CO (X ¹A₁) and O (³P) + H₂CO (a ³A''). Dissociation proceeds on multiple singlet potential energy surfaces that are coupled by two regions of conical intersection (CoIn). Velocity map imaging (VMI) studies reveal a bimodal total kinetic energy release (TKER) distribution for the O (¹D) + H₂CO (X ¹A₁) products with the major and minor components accounting for ca. 40% and ca. 20% on average of the available energy (E_avl), respectively. The unexpected low TKER component corresponds to highly internally excited H₂CO (X ¹A₁) products accommodating ca. 80% of E_avl. Full dimensional trajectory calculations suggest that the bimodal TKER distribution of the O (¹D) + H₂CO (X ¹A₁) products originates from two different dynamical pathways: a primary pathway (69%) evolving through one CoIn region to products and a smaller component (20%) sampling both CoIn regions enroute to products. Those that access both CoIn regions likely give rise to the more highly internally excited H₂CO (X ¹A₁) products. The remaining trajectories (11%) dissociate to O (³P) + H₂CO (a ³A'') products after traversing through both CoIn regions. The complementary experimental and theoretical investigation provides insight on the photodissociation of CH₂OO via multiple dissociation pathways through two regions of CoIn that control the branching and energy distributions of products.