Encoding of vinylidene isomerization in its anion photoelectron spectrum

dc.contributor.authorDeVine, Jessalyn A
dc.contributor.authorWeichman, Marissa L
dc.contributor.authorLaws, Benjamin
dc.contributor.authorChang, Jing
dc.contributor.authorBabin, Mark C
dc.contributor.authorBalerdi, Garikoitz
dc.contributor.authorXie, Changjian
dc.contributor.authorMalbon, Christopher L
dc.contributor.authorLineberger, William Carl
dc.contributor.authorYarkony, David
dc.contributor.authorField, Robert
dc.contributor.authorGibson, Stephen
dc.contributor.authorMa, Jianyi
dc.contributor.authorGuo, Hua
dc.contributor.authorNeumark, Daniel
dc.date.accessioned2021-06-15T04:01:41Z
dc.date.issued2017
dc.date.updated2020-11-23T10:29:03Z
dc.description.abstractVinylidene-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 H2CCˉ and D2CCˉ 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 ν6 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 D2CCen_AU
dc.description.sponsorshipThe 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).en_AU
dc.format.mimetypeapplication/pdfen_AU
dc.identifier.issn1095-9203en_AU
dc.identifier.urihttp://hdl.handle.net/1885/237352
dc.language.isoen_AUen_AU
dc.publisherAmerican Association for the Advancement of Scienceen_AU
dc.relationhttp://purl.org/au-research/grants/arc/DP160102585en_AU
dc.rights© The Authors, some rights reserved; exclusive licensee American Association for the Advancement of Scienceen_AU
dc.sourceScienceen_AU
dc.titleEncoding of vinylidene isomerization in its anion photoelectron spectrumen_AU
dc.typeJournal articleen_AU
local.bibliographicCitation.issue6361en_AU
local.bibliographicCitation.lastpage339en_AU
local.bibliographicCitation.startpage336en_AU
local.contributor.affiliationDeVine, Jessalyn A, University of Californiaen_AU
local.contributor.affiliationWeichman, Marissa L, University of Californiaen_AU
local.contributor.affiliationLaws, Benjamin, College of Science, ANUen_AU
local.contributor.affiliationChang, Jing, Sichuan Universityen_AU
local.contributor.affiliationBabin, Mark C, University of Californiaen_AU
local.contributor.affiliationBalerdi, Garikoitz, Universidad Complutense de Madrid (Unidad Asociada I+D+I CSIC)en_AU
local.contributor.affiliationXie, Changjian, University of New Mexicoen_AU
local.contributor.affiliationMalbon, Christopher L, Johns Hopkins Universityen_AU
local.contributor.affiliationLineberger, William Carl, University of Coloradoen_AU
local.contributor.affiliationYarkony, David, Johns Hopkins Universityen_AU
local.contributor.affiliationField, Robert, Massachusetts Institute of Technologyen_AU
local.contributor.affiliationGibson, Stephen, College of Science, ANUen_AU
local.contributor.affiliationMa, Jianyi, Sichuan Universityen_AU
local.contributor.affiliationGuo, Hua, University of New Mexicoen_AU
local.contributor.affiliationNeumark, Daniel, University of California, Berkeleyen_AU
local.contributor.authoremailu5520109@anu.edu.auen_AU
local.contributor.authoruidLaws, Benjamin, u5520109en_AU
local.contributor.authoruidGibson, Stephen, u8601433en_AU
local.description.embargo2099-12-31
local.description.notesImported from ARIESen_AU
local.identifier.absfor030500 - ORGANIC CHEMISTRYen_AU
local.identifier.ariespublicationu5234101xPUB39en_AU
local.identifier.citationvolume358en_AU
local.identifier.doi10.1126/science.aao1905en_AU
local.identifier.scopusID2-s2.0-85032470636
local.identifier.uidSubmittedByu5234101en_AU
local.publisher.urlhttp://www.sciencemag.org/en_AU
local.type.statusPublished Versionen_AU

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