The reactions of F(2P)+ketene and F(2P)+ketene-d2 were studied in a flow reactor. Spectra of the radical products CH2F, CD2F, CH, CF, and atomic carbon were detected between 292–395 nm by resonance enhanced multiphoton ionization (REMPI) mass spectrometry. Fluoromethyl radicals were identified as a major product of the F+ketene elementary reaction. REMPI spectra of fluoromethyl radicals originated from two-photon preparation of 3p, 4p, and 5p Rydberg states (quantum defect ∼0.6). Absorption of a third laser photon ionized the radicals, a 2+1 REMPI mechanism. Rydberg band origins were observed in CH2F at ν00=52 863, 63 275, and 67 265 cm−1 and in CD2F at ν00=52 786, 63 195, and 67 186 cm−1. A normal mode analysis revealed the vibrational frequencies of the C–F stretch, CH2 scissors, and out-of-plane bending modes in the Rydberg states. The ground state out-of-plane bending frequency in CH2F is 260(30) cm−1 and in CD2F it is 170(30) cm−1. CH radicals were generated by the photolysis of ketene and observed at ∼311 nm by two-photon excitation through the D 2Π(v′=2) ←←X 2Πr band. The reaction mechanism that generated the CF radicals was not determined. The REMPI CF radical spectrum generated by a 2+1 photon mechanism appeared as a series of bandheads described by the constants ν00=∼52 572 cm−1, ωe =1820 cm−1, and ωexe =−18.2 cm−1.

Chemischer InformationsdienstVolume 17, Issue 39 Physical Organic Chemistry ChemInform Abstract: Multiphoton Ionization Spectroscopy and Vibrational Analysis of a 3p Rydberg State of the Hydroxymethyl Radical C. S. DULCEY, C. S. DULCEYSearch for more papers by this authorJ. W. HUDGENS, J. W. HUDGENSSearch for more papers by this author C. S. DULCEY, C. S. DULCEYSearch for more papers by this authorJ. W. HUDGENS, J. W. HUDGENSSearch for more papers by this author First published: September 30, 1986 https://doi.org/10.1002/chin.198639036AboutPDF ToolsRequest permissionExport citationAdd to favoritesTrack citation ShareShare Give accessShare full text accessShare full-text accessPlease review our Terms and Conditions of Use and check box below to share full-text version of article.I have read and accept the Wiley Online Library Terms and Conditions of UseShareable LinkUse the link below to share a full-text version of this article with your friends and colleagues. Learn more.Copy URL Share a linkShare onEmailFacebookTwitterLinkedInRedditWechat No abstract is available for this article. References C. S. DULCEY, J. W. HUDGENS, Multiphoton Ionization Spectroscopy and Vibrational Analysis of a 3p Rydberg State of the Hydroxymethyl Radical, J. Chem. Phys., 1986, 84, 5262. DOI: 10.1063/1.449935; 10.1063/1.449935 CASWeb of Science®Google Scholar Volume17, Issue39September 30, 1986 ReferencesRelatedInformation

The resonance enhanced multiphoton ionization (REMPI) spectra of CH2OH, CH2OD, CD2OH, and CD2OD between 420–495 nm are reported. Analysis of the excited state vibrational band progressions shows that the spectrum originates from simultaneous two photon absorption to form a 3p Rydberg state (ν00=40 064 cm−1) of the radical. Absorption of a third photon ionized the radical. A normal mode analysis of the REMPI spectra enabled assignments of six active vibrational modes in the excited state. The no isomerization of methoxy radicals into hydroxymethyl radicals was observed. The experimental measurement uncertainty limits this isomerization rate to less than 2.9 s−1 at 300 K.

ADVERTISEMENT RETURN TO ISSUEPREVArticleNEXTObservation of the 3s 2A1 Rydberg states of allyl and 2-methylallyl radicals with multiphoton ionization spectroscopyJeffrey W. Hudgens and C. S. DulceyCite this: J. Phys. Chem. 1985, 89, 8, 1505–1509Publication Date (Print):April 1, 1985Publication History Published online1 May 2002Published inissue 1 April 1985https://pubs.acs.org/doi/10.1021/j100254a039https://doi.org/10.1021/j100254a039research-articleACS PublicationsRequest reuse permissionsArticle Views136Altmetric-Citations49LEARN ABOUT THESE METRICSArticle Views are the COUNTER-compliant sum of full text article downloads since November 2008 (both PDF and HTML) across all institutions and individuals. These metrics are regularly updated to reflect usage leading up to the last few days.Citations are the number of other articles citing this article, calculated by Crossref and updated daily. Find more information about Crossref citation counts.The Altmetric Attention Score is a quantitative measure of the attention that a research article has received online. Clicking on the donut icon will load a page at altmetric.com with additional details about the score and the social media presence for the given article. Find more information on the Altmetric Attention Score and how the score is calculated. Share Add toView InAdd Full Text with ReferenceAdd Description ExportRISCitationCitation and abstractCitation and referencesMore Options Share onFacebookTwitterWechatLinked InRedditEmail Other access options Get e-Alerts

Chemischer InformationsdienstVolume 14, Issue 40 Physical Organic Chemistry ChemInform Abstract: DETECTION OF HYDROXYMETHYL (CH2OH) RADICALS BY RESONANCE-ENHANCED MULTIPHOTON IONIZATION SPECTROSCOPY C. S. DULCEY, C. S. DULCEYSearch for more papers by this authorJ. W. HUDGENS, J. W. HUDGENSSearch for more papers by this author C. S. DULCEY, C. S. DULCEYSearch for more papers by this authorJ. W. HUDGENS, J. W. HUDGENSSearch for more papers by this author First published: October 4, 1983 https://doi.org/10.1002/chin.198340058AboutPDF ToolsRequest permissionExport citationAdd to favoritesTrack citation ShareShare Give accessShare full text accessShare full-text accessPlease review our Terms and Conditions of Use and check box below to share full-text version of article.I have read and accept the Wiley Online Library Terms and Conditions of UseShareable LinkUse the link below to share a full-text version of this article with your friends and colleagues. Learn more.Copy URL Share a linkShare onEmailFacebookTwitterLinked InRedditWechat No abstract is available for this article. Volume14, Issue40October 4, 1983 RelatedInformation