UV photodissociation dynamics of the acetone oxide Criegee intermediate: experiment and theory

The photodissociation dynamics of the dimethyl-substituted acetone oxide Criegee intermediate [(CH₃)₂COO] is characterized following electronic excitation to the bright ¹ππ* state, which leads to O (¹D) + acetone [(CH₃)₂CO, S₀] products. The UV action spectrum of (CH₃)₂COO recorded with O (¹D) detection under jet-cooled conditions is broad, unstructured, and essentially unchanged from the corresponding electronic absorption spectrum obtained using a UV-induced depletion method. This indicates that UV excitation of (CH₃)₂COO leads predominantly to the O (¹D) product channel. A higher energy O (³P) + (CH₃)₂CO (T₁) product channel is not observed, although it is energetically accessible. In addition, complementary MS-CASPT2 trajectory surface-hopping (TSH) simulations indicate minimal population leading to the O (³P) channel and non-unity overall probability for dissociation (within 100 fs). Velocity map imaging of the O (¹D) products is utilized to reveal the total kinetic energy release (TKER) distribution upon photodissociation of (CH₃)₂COO at various UV excitation energies. Simulation of the TKER distributions is performed using a hybrid model that combines an impulsive model with a statistical component, the latter reflecting the longer-lived (>100 fs) trajectories identified in the TSH calculations. The impulsive model accounts for vibrational activation of (CH₃)₂CO arising from geometrical changes between the Criegee intermediate and the carbonyl product, indicating the importance of CO stretch, CCO bend, and CC stretch along with activation of hindered rotation and rock of the methyl groups in the (CH₃)₂CO product. Detailed comparison is also made with the TKER distribution arising from photodissociation dynamics of CH₂OO upon UV excitation.