{"status":"ok","message-type":"work","message-version":"1.0.0","message":{"indexed":{"date-parts":[[2026,10,6]],"date-time":"2026-10-06T15:56:36Z","timestamp":1791302196178,"version":"4.1.0"},"reference-count":54,"publisher":"American Chemical Society (ACS)","issue":"39","license":[{"start":{"date-parts":[[2026,9,23]],"date-time":"2026-09-23T00:00:00Z","timestamp":1790121600000},"content-version":"vor","delay-in-days":0,"URL":"https:\/\/creativecommons.org\/licenses\/by-nc-nd\/4.0\/"}],"funder":[{"DOI":"10.13039\/501100001691","name":"Japan Society for the Promotion of Science","doi-asserted-by":"publisher","award":["21H05430"],"award-info":[{"award-number":["21H05430"]}],"id":[{"id":"10.13039\/501100001691","id-type":"DOI","asserted-by":"publisher"}]},{"DOI":"10.13039\/501100001691","name":"Japan Society for the Promotion of Science","doi-asserted-by":"publisher","award":["23H03992"],"award-info":[{"award-number":["23H03992"]}],"id":[{"id":"10.13039\/501100001691","id-type":"DOI","asserted-by":"publisher"}]}],"content-domain":{"domain":[],"crossmark-restriction":false},"short-container-title":[],"published-print":{"date-parts":[[2026,10,6]]},"abstract":"<jats:title>Abstract<\/jats:title>\n                  <jats:p>We examined the effect of nonplanarization of the amide framework on the photodissociation dynamics of N,N-dimethylformamide (DMF, (CH3)2N(CO)H) at 213 nm. The final state distributions of the photodissociation products in the N\u2013CO and N\u2013CH3 bond dissociation pathways were measured using laser-induced fluorescence and resonance-enhanced multiphoton ionization spectroscopy. The formation of highly vibrationally excited HCO products over the dissociation threshold was confirmed by detecting the H and CO products of the sequential dissociation. The vibrational and rotational excitation of HCO indicated the nonplanar deformation in the 21A\u2032(\u03c0\u03c0*) excited state of DMF. The reaction route through the fast internal conversion (21A\u2032(\u03c0\u03c0*) \u2192 11A\u2033(n\u03c0*)) facilitated at the nonplanar structure was demonstrated with theoretical calculations. In contrast, the energy partitioning of the N\u2013CH3 bond dissociation pathway was found to be statistically distributed. We attributed the relatively slow mechanism to an energy barrier on the dissociation route based on the theoretical potential energy surface of 21A\u2032(\u03c0\u03c0*).<\/jats:p>","DOI":"10.1021\/acsomega.6c05518","type":"journal-article","created":{"date-parts":[[2026,9,23]],"date-time":"2026-09-23T11:01:50Z","timestamp":1790161310000},"page":"59415-59424","source":"Crossref","is-referenced-by-count":0,"title":["State Distributions\nof HCO and CH3 Products\nin the Ultraviolet Photodissociation of\n                    <i>N<\/i>\n                    ,\n                    <i>N<\/i>\n                    -Dimethylformamide"],"prefix":"10.1021","volume":"11","author":[{"given":"Momiji","family":"Karino","sequence":"first","affiliation":[{"name":"Hiroshima University , , Kagamiyama 1-3-1 , , ,","place":["Higashi-Hiroshima, Hiroshima, Japan, 739-8526"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Kosuke","family":"Inoue","sequence":"additional","affiliation":[{"name":"Hiroshima University , , Kagamiyama 1-3-1 , , ,","place":["Higashi-Hiroshima, Hiroshima, Japan, 739-8526"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Ryo","family":"Shinohara","sequence":"additional","affiliation":[{"name":"Hiroshima University , , Kagamiyama 1-3-1 , , ,","place":["Higashi-Hiroshima, Hiroshima, Japan, 739-8526"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-0823-9636","authenticated-orcid":true,"given":"Katsuyoshi","family":"Yamasaki","sequence":"additional","affiliation":[{"name":"Hiroshima University , , Kagamiyama 1-3-1 , , ,","place":["Higashi-Hiroshima, Hiroshima, Japan, 739-8526"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0001-9684-1258","authenticated-orcid":true,"given":"Hiroshi","family":"Kohguchi","sequence":"additional","affiliation":[{"name":"Hiroshima University , , Kagamiyama 1-3-1 , , ,","place":["Higashi-Hiroshima, Hiroshima, Japan, 739-8526"]}],"role":[{"vocabulary":"crossref","role":"author"}]}],"member":"316","published-online":{"date-parts":[[2026,9,23]]},"reference":[{"key":"2026100610500388100_cit1","doi-asserted-by":"publisher","first-page":"1400","DOI":"10.1021\/jp963765v","article-title":"High-Level Electron Correlation Calculations on Formamide\nand the Resonance Model","volume":"101","author":"Fogarasi","year":"1997","journal-title":"J. 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Mol.\nSpectrosc."},{"key":"2026100610500388100_cit4","doi-asserted-by":"publisher","first-page":"326","DOI":"10.1007\/s10812-011-9466-1","article-title":"Modeling of Structures and Calculation of IR Vibrational\nSpectra of N,N-Dimethylformamide Dimers by Density Functional Theory","volume":"78","author":"Shundalau","year":"2011","journal-title":"J. Appl. Spectrosc."},{"key":"2026100610500388100_cit5","doi-asserted-by":"publisher","DOI":"10.1063\/1.5006126","article-title":"Spectroscopy of N,N-Dimethylformamide\nin the VUV and IR Regions: Experimental and Computational Studies","volume":"147","author":"Shastri","year":"2017","journal-title":"J. Chem. Phys."},{"key":"2026100610500388100_cit6","doi-asserted-by":"publisher","DOI":"10.1063\/1.4983704","article-title":"Photofragmentation Dynamics of N,N-Dimethylformamide\nFollowing Excitation at 193 nm","volume":"147","author":"Lipciuc","year":"2017","journal-title":"J. Chem. 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Spectrosc."},{"key":"2026100610500388100_cit43","doi-asserted-by":"publisher","first-page":"90","DOI":"10.1039\/df9633500090","article-title":"Electronic\nabsorption spectra of\nHCO and DCO radicals","volume":"35","author":"Johns","year":"1963","journal-title":"Discuss. Faraday Soc."},{"key":"2026100610500388100_cit44","doi-asserted-by":"publisher","first-page":"8789","DOI":"10.1063\/1.481533","article-title":"The Predissociation\nMechanism of the the B\u03032A\u2032 State of HCO via\nthe Conical Intersection with the X\u03032A\u2032 State","volume":"112","author":"Manaa","year":"2000","journal-title":"J. Chem. 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Phys."},{"key":"2026100610500388100_cit51","doi-asserted-by":"publisher","DOI":"10.1063\/1.2135772","article-title":"IR\/UV Double Resonant Spectroscopy\nof the Methyl Radical: Determination of \u03bd3 in the\n3pz Rydberg State","volume":"123","author":"Fu","year":"2005","journal-title":"J. Chem. Phys."},{"key":"2026100610500388100_cit52","doi-asserted-by":"publisher","first-page":"5284","DOI":"10.1063\/1.443797","article-title":"Difference\nFrequency Laser Spectroscopy of the \u03bd3-Band of the\nCH3 Radical","volume":"77","author":"Amano","year":"1982","journal-title":"J. Chem. Phys."},{"key":"2026100610500388100_cit53","doi-asserted-by":"publisher","first-page":"1871","DOI":"10.1021\/acs.jpca.4c00001","article-title":"N-H and N-C Bond Dissociation\nPathways in Ultraviolet Photodissociation of Dimethylamine","volume":"128","author":"Wangchingchai","year":"2024","journal-title":"J. Phys. Chem. 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