期刊
CHEMPHYSCHEM
卷 14, 期 16, 页码 3687-3697出版社
WILEY-V C H VERLAG GMBH
DOI: 10.1002/cphc.201300713
关键词
iodine; photolysis; reaction mechanisms; structural dynamics; X-ray scattering
资金
- Institute for Basic Science (IBS)
- PRESTO/JST
- National Research Foundation of Korea (NRF) [2007-0056095]
- Korean government (MSIP)
- Inha University [INHA-48581]
- Grants-in-Aid for Scientific Research [25107527] Funding Source: KAKEN
- Ministry of Science, ICT & Future Planning, Republic of Korea [IBS CA1301] Funding Source: Korea Institute of Science & Technology Information (KISTI), National Science & Technology Information Service (NTIS)
The mechanism of a photochemical reaction involves the formation and dissociation of various short-lived species on ultrafast timescales and therefore its characterization requires detailed structural information on the transient species. By making use of a structurally sensitive X-ray probe, time-resolved X-ray liquidography (TRXL) can directly elucidate the structures of reacting molecules in the solution phase and thus determine the comprehensive reaction mechanism with high accuracy. In this work, by performing TRXL measurements at two different wavelengths (400 and 267 nm), the reaction mechanism of I-3(-) photolysis, which changes subtly depending on the excitation wavelength, is elucidated. Upon 400 nm photoexcitation, the I-3(-) ion dissociates into I-2(-) and I. By contrast, upon 267 nm photoexcitation, the I-3(-) ion undergoes both two-body dissociation (I-2(-)+I) and three-body dissociation (I-+2I) with 7:3 molar ratio. At both excitation wavelengths, all the transient species ultimately disappear in 80 ns by recombining to form the I-3(-) ion nongeminately. In addition to the reaction dynamics of solute species, the results reveal the transient structure of the solute/solvent cage and the changes in solvent density and temperature as a function of time.
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