{"status":"ok","message-type":"work","message-version":"1.0.0","message":{"indexed":{"date-parts":[[2026,9,3]],"date-time":"2026-09-03T11:14:23Z","timestamp":1788434063415,"version":"build-2803163510"},"reference-count":56,"publisher":"American Chemical Society (ACS)","issue":"50","license":[{"start":{"date-parts":[[2015,7,30]],"date-time":"2015-07-30T00:00:00Z","timestamp":1438214400000},"content-version":"vor","delay-in-days":10,"URL":"https:\/\/pubs.acs.org\/page\/policy\/authorchoice_ccby_termsofuse.html"}],"funder":[{"DOI":"10.13039\/501100000266","name":"Engineering and Physical Sciences Research Council","doi-asserted-by":"publisher","award":["EP\/J002534\/2"],"award-info":[{"award-number":["EP\/J002534\/2"]}],"id":[{"id":"10.13039\/501100000266","id-type":"DOI","asserted-by":"publisher"}]},{"DOI":"10.13039\/501100000781","name":"European Research Council","doi-asserted-by":"publisher","award":["290966"],"award-info":[{"award-number":["290966"]}],"id":[{"id":"10.13039\/501100000781","id-type":"DOI","asserted-by":"publisher"}]}],"content-domain":{"domain":[],"crossmark-restriction":false},"short-container-title":[],"published-print":{"date-parts":[[2015,12,17]]},"abstract":"<jats:title>Abstract<\/jats:title>\n                  <jats:p>Transient electronic and vibrational absorption spectroscopy unravel the mechanisms and dynamics of bimolecular reactions of CN radicals with acetone in deuterated chloroform solutions. The CN radicals are produced by ultrafast ultraviolet photolysis of dissolved ICN. Two reactive forms of CN radicals are distinguished by their electronic absorption bands: \u201cfree\u201d (uncomplexed) CN radicals, and \u201csolvated\u201d CN radicals that are complexed with solvent molecules. The lifetimes of the free CN radicals are limited to a few picoseconds following their photolytic production because of geminate recombination to ICN and INC, complexation with CDCl3 molecules, and reaction with acetone. The acetone reaction occurs with a rate coefficient of (8.0 \u00b1 0.5) \u00d7 1010 M\u20131 s\u20131 and transient vibrational spectra in the C\u2550N and C\u2550O stretching regions reveal that both the nascent HCN and 2-oxopropyl (CH3C(O)CH2) radical products are vibrationally excited. The rate coefficient for the reaction of solvated CN with acetone is 40 times slower than for free CN, with a rate coefficient of (2.0 \u00b1 0.9) \u00d7 109 M\u20131 s\u20131 obtained from the rise in the HCN product v1(C\u2550N stretch) IR absorption band. Evidence is also presented for CN complexes with acetone that are more strongly bound than the CN\u2013CDCl3 complexes because of CN interactions with the carbonyl group. The rates of reactions of these more strongly associated radicals are slower still.<\/jats:p>","DOI":"10.1021\/acs.jpca.5b05624","type":"journal-article","created":{"date-parts":[[2015,7,20]],"date-time":"2015-07-20T15:40:02Z","timestamp":1437406802000},"page":"12090-12101","source":"Crossref","is-referenced-by-count":7,"title":["Vibrational Excitation of Both Products of the Reaction\nof CN Radicals with Acetone in Solution"],"prefix":"10.1021","volume":"119","author":[{"given":"Greg T.","family":"Dunning","sequence":"first","affiliation":[{"name":"University of Bristol , , Cantock\u2019s Close , ,","place":["Bristol, U.K., BS8 1TS"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Thomas J.","family":"Preston","sequence":"additional","affiliation":[{"name":"University of Bristol , , Cantock\u2019s Close , ,","place":["Bristol, U.K., BS8 1TS"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Stuart J.","family":"Greaves","sequence":"additional","affiliation":[{"name":"Heriot-Watt University , , ,","place":["Edinburgh, U.K., EH14 4AS"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Gregory M.","family":"Greetham","sequence":"additional","affiliation":[{"name":"Rutherford Appleton Laboratory , , , ,","place":["Harwell Oxford, Didcot, Oxfordshire, U.K., OX11 0QX"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Ian P.","family":"Clark","sequence":"additional","affiliation":[{"name":"Rutherford Appleton Laboratory , , , ,","place":["Harwell Oxford, Didcot, Oxfordshire, U.K., OX11 0QX"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Andrew J.","family":"Orr-Ewing","sequence":"additional","affiliation":[{"name":"University of Bristol , , Cantock\u2019s Close , ,","place":["Bristol, U.K., BS8 1TS"]}],"role":[{"vocabulary":"crossref","role":"author"}]}],"member":"316","published-online":{"date-parts":[[2015,7,20]]},"reference":[{"key":"2026090306171625400_cit1","doi-asserted-by":"publisher","first-page":"090901","DOI":"10.1063\/1.4866761","article-title":"Bimolecular\nChemical Reaction Dynamics in Solution","volume":"140","author":"Orr-Ewing","year":"2014","journal-title":"J. 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