Photodissociation dynamics and UV absorption spectrum of acetone oxide (CH3)2COO

Abstract

The photodynamics and B¹A′ ← X¹A′ absorption spectrum of acetone oxide, (CH₃)₂COO, 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, CH₂OO, it is found that the vibronic coupling between the B and C states of (CH₃)₂COO plays an essential role in reproducing the experimental absorption spectrum. Time-dependent electronic populations reveal a faster decay than for the smaller system CH₂OO. 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 CH₂OO.