@article{87255794ab87495dbc7160f8e459658d,
title = "Encoding of vinylidene isomerization in its anion photoelectron spectrum",
abstract = "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 n6 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.",
author = "DeVine, {Jessalyn A.} and Weichman, {Marissa L.} and Benjamin Laws and Jing Chang and Babin, {Mark C.} and Garikoitz Balerdi and Changjian Xie and Malbon, {Christopher L.} and Lineberger, {W. Carl} and Yarkony, {David R.} and Field, {Robert W.} and Gibson, {Stephen T.} and Jianyi Ma and Hua Guo and Neumark, {Daniel M.}",
note = "Funding Information: The experimental part of this research was funded by the Air Force Office of Scientific Research (FA9550-16-1-0097 to D.M.N.) and the Australian Research Council Discovery Project (DP160102585 to S.T.G.). M.L.W. thanks the National Science Foundation for a graduate research fellowship. Experimental data are available in the supplementary materials. Theoretical work was funded by the National Natural Science Foundation of China (91441107 to J.M.), the Air Force Office of Scientific Research (FA9550-15-1-0305 to H.G.), and the National Science Foundation (CHE-1361121 to D.R.Y.). R.W.F. gratefully acknowledges the Department of Energy, Office of Science, Chemical Sciences Geosciences and Biosciences Division of the Basic Energy Sciences Office (DE-FG0287ER13671). W.C.L. thanks the National Science Foundation JILA Physics Frontier Center (PHY1128544), and G.B. acknowledges the Spanish Ministry of Economy and Competitiveness (EEBB-I-16-11350 and BES-2013-063562).",
year = "2017",
month = oct,
day = "20",
doi = "10.1126/science.aao1905",
language = "English (US)",
volume = "358",
pages = "336--339",
journal = "Science",
issn = "0036-8075",
publisher = "American Association for the Advancement of Science",
number = "6361",
}