Encoding of vinylidene isomerization in its anion photoelectron spectrum

Vinylidene-acetylene isomerization is the prototypical example of a 1,2-hydrogen shift, one of the most important classes of isomerization reactions in organic chemistry. This reaction was investigated with quantum state specificity by high-resolution photoelectron spectroscopy of the vinylidene anions H 2 CCˉ and D 2 CCˉ and quantum dynamics calculations. Peaks in the photoelectron spectra are considerably narrower than in previous work and reveal subtleties in the isomerization dynamics of neutral vinylidene, as well as vibronic coupling with an excited state of vinylidene. Comparison with theory permits assignment of most spectral features to eigenstates dominated by vinylidene character. However, excitation of the ν 6 in-plane rocking mode in H 2 CC results in appreciable tunneling-facilitated mixing with highly vibrationally excited states of acetylene, leading to broadening and/or spectral fine structure that is largely suppressed for analogous vibrational levels of D 2 CC.