Theoretical Analysis of the Formylmethylene Anion Photoelectron Spectrum: Importance of Wolff Rearrangement Dynamics

Abstract

Photoelectron spectroscopy of a molecular anion is very useful for investigating the transition state and intermediate regions on the reactive potential energy surfaces of a neutral system. In this work, we theoretically analyzed the previously measured photoelectron spectrum of the formylmethylene anion, HCCHO − . We simulated the photoelectron spectra for both the singlet and triplet states using the semiclassical method with quantum nuclear densities and Franck−Condon factor calculations with harmonic vibrational analysis. We also performed real-time quantum dynamics calculations to elucidate the importance of the Wolff rearrangement process, which leads to the stable product ketene from the carbene intermediate on the neutral singlet potential energy surface.