Encoding of vinylidene isomerization in its anion photoelectron spectrum

Jessalyn A. DeVine, Marissa L. Weichman, Benjamin Laws, Jing Chang, Mark C. Babin, Garikoitz Balerdi, Changjian Xie, Christopher L. Malbon, W. Carl Lineberger, David R. Yarkony, Robert W. Field, Stephen T. Gibson, Jianyi Ma, Hua Guo, Daniel M. Neumark

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20 Scopus citations

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.

Original languageEnglish (US)
Pages (from-to)336-339
Number of pages4
JournalScience
Volume358
Issue number6361
DOIs
StatePublished - Oct 20 2017
Externally publishedYes

All Science Journal Classification (ASJC) codes

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    DeVine, J. A., Weichman, M. L., Laws, B., Chang, J., Babin, M. C., Balerdi, G., Xie, C., Malbon, C. L., Lineberger, W. C., Yarkony, D. R., Field, R. W., Gibson, S. T., Ma, J., Guo, H., & Neumark, D. M. (2017). Encoding of vinylidene isomerization in its anion photoelectron spectrum. Science, 358(6361), 336-339. https://doi.org/10.1126/science.aao1905