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- 저자 : Grolimund, Daniel (검색결과 1 건)
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Kim, Kyung Hwan,Kim, Jeongho,Oang, Key Young,Lee, Jae Hyuk,Grolimund, Daniel,Milne, Christopher J.,Penfold, Thomas J.,Johnson, Steven L.,Galler, Andreas,Kim, Tae Wu,Kim, Jong Goo,Suh, Deokbeom,Moon, J The Royal Society of Chemistry 2015 Physical chemistry chemical physics Vol.17 No.36
<P>Identifying the intermediate species along a reaction pathway is a first step towards a complete understanding of the reaction mechanism, but often this task is not trivial. There has been a strong on-going debate: which of the three intermediates, the CHI<SUB>2</SUB> radical, the CHI<SUB>2</SUB>–I isomer, and the CHI<SUB>2</SUB><SUP>+</SUP> ion, is the dominant intermediate species formed in the photolysis of iodoform (CHI<SUB>3</SUB>)? Herein, by combining time-resolved X-ray liquidography (TRXL) and time-resolved X-ray absorption spectroscopy (TR-XAS), we present strong evidence that the CHI<SUB>2</SUB> radical is dominantly formed from the photolysis of CHI<SUB>3</SUB> in methanol at 267 nm within the available time resolution of the techniques (∼20 ps for TRXL and ∼100 ps for TR-XAS). The TRXL measurement, conducted using the time-slicing scheme, detected no CHI<SUB>2</SUB>–I isomer within our signal-to-noise ratio, indicating that, if formed, the CHI<SUB>2</SUB>–I isomer must be a minor intermediate. The TR-XAS transient spectra measured at the iodine L<SUB>1</SUB> and L<SUB>3</SUB> edges support the same conclusion. The present work demonstrates that the application of these two complementary time-resolved X-ray methods to the same system can provide a detailed understanding of the reaction mechanism.</P> <P>Graphic Abstract</P><P>We identify a major transient species formed in the photolysis of CHI<SUB>3</SUB> by combining time-resolved X-ray liquidography (TRXL) and time-resolved X-ray absorption spectroscopy (TR-XAS). <IMG SRC='http://pubs.rsc.org/services/images/RSCpubs.ePlatform.Service.FreeContent.ImageService.svc/ImageService/image/GA?id=c5cp03686k'> </P>
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