UV Absorption Spectroscopy of the Conformer-Dependent Reactivity of the Four Carbon Criegee Intermediate of Methyl Vinyl Ketone Oxide: An Ab initio Quantum Dynamics Study.

Abstract

An extended theoretical analysis of the photodissociation dynamics of the four-carbon Criegee intermediate (CH2═CH(CH3)COO) or methyl vinyl ketone oxide, which has four conformers, following excitation to the B state, is presented. Our analysis relies on multireference electronic wave functions combined with a wavepacket propagation treatment for the two coupled B1A' and C1A' electronic states and two nuclear degrees of freedom. For each conformer, the 2D model depends on potential energy surfaces (PESs) along the O-O and C-O-O bending modes for the two lowest excited states, B1A' and C1A', and is sufficiently accurate to reproduce the experimental B1A' ← X1A' absorption spectrum with unprecedented accuracy. It is found that the roles of each conformer are essential in producing a cumulative spectrum, which is close to the recent experimental spectrum. The anti-trans and anti-cis conformers make contributions at the longer and shorter wavelengths of the cumulative spectrum, respectively, while the syn-cis and syn-trans conformers have contributions in the middle wavelength range of the cumulative spectrum of MVK-oxide. The existence of a deep well for each conformer on the PESs of the (diabatic) B state causes a considerable amount of the wavepacket to be reflected by the B state wells, which can explain the oscillatory structures appearing in the long wavelength range of 360-480 nm of the spectrum. The weakly avoided crossings between the B-state and C-state PESs of each conformer appearing within the range of 2.80-3.08 eV excitation energy cause considerable disturbance in the vibronic fine structure of the bands. The results give novel insight into the complex interactions governing this intriguing process.