Journal
SCIENCE
Volume 358, Issue 6361, Pages 336-339Publisher
AMER ASSOC ADVANCEMENT SCIENCE
DOI: 10.1126/science.aao1905
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Funding
- Air Force Office of Scientific Research [FA9550-16-1-0097, FA9550-15-1-0305]
- Australian Research Council Discovery Project [DP160102585]
- National Science Foundation [CHE-1361121]
- National Natural Science Foundation of China [91441107]
- Department of Energy, Office of Science, Chemical Sciences Geosciences and Biosciences Division of the Basic Energy Sciences Office [DE-FG0287ER13671]
- National Science Foundation JILA Physics Frontier Center [PHY1128544]
- Spanish Ministry of Economy and Competitiveness [EEBB-I-16-11350, BES-2013-063562]
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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 H2CC- and D2CC- 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 v(6) in-plane rocking mode in H2CC 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 D2CC.
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