Correlated quantum treatment of the photodissociation dynamics of formaldehyde oxide CH₂OO

An extended theoretical analysis of the photodissociation of the smallest Criegee intermediate CH₂OO following excitation to the B state is presented. It relies on explicitly correlated multireference electronic wavefunctions combined with a quantum dynamical treatment for two interacting (B-C) electronic states and three coupled nuclear degrees of freedom. The 3D model relies on PESs along the O-O and C-O stretching as well as C-O-O bending modes for the two lowest excited states with A' symmetry, and is sufficiently accurate to reproduce the experimental B¹A'-X¹A' absorption spectrum, especially at the low-energy range to unprecedented accuracy. The existence of a deep well (∼0.4 eV) on the (diabatic) B state causes a considerable amount of the wavepacket to be reflected by the B state well, which can explain the vibronic structures appearing in the long wavelength range of 360-470 nm of the spectrum. The main progression appearing in the energy range from 360 to 470 nm is assigned to the O-O stretching mode while finer details are affected by couplings to the C-O stretching and C-O-O bending modes. The weakly avoided crossing between the B-state and C-state potential energy surfaces appearing near 3.1 eV excitation energy (for RS2-F12 method) causes considerable disturbance in the vibronic fine structure of the bands. The description of the latter is quite strongly affected by the type of electron correlation treatment adopted, either fully variational (MRCI type) or perturbation theoretic (RS2 type). The results give novel insight into the complex interactions governing that intriguing process.