Photodissociation dynamics and UV absorption spectrum of acetone oxide (CH 3 ) 2 COO.

The photodynamics and B 1 A' ← X 1 A' absorption spectrum of acetone oxide, (CH 3 ) 2 COO, are studied theoretically from first principles. The underlying adiabatic potential energy curves (and surfaces) are computed by a second-order multireference perturbation theory method and diabatized using a diabatization by ansatz scheme. To confirm the results, for selected geometries EOM-CCSD and XMS-RS2C calculations were also performed. The dynamical calculation rests on the multi-configuration time-dependent Hartree wavepacket propagation method. The experimental absorption spectrum is reproduced satisfactorily. This result serves to validate the Hamiltonian model built within the quasi-diabatic representation. Contrary to the smallest Criegee intermediate, CH 2 OO, it is found that the vibronic coupling between the B and C states of (CH 3 ) 2 COO plays an essential role in reproducing the experimental absorption spectrum. Time-dependent electronic populations reveal a faster decay than for the smaller system CH 2 OO. This is interpreted in terms of the stronger coupling between the B and C states in the larger system leading to a shorter lifetime for the B state than in CH 2 OO.