Identifying the major intermediate species by combining time-resolved X-ray solution scattering and X-ray absorption spectroscopy

Kyung Hwan Kim, Jeongho Kim, Key Young Oang, Jae Hyuk Lee, Daniel Grolimund, Christopher J. Milne, Thomas J. Penfold, Steven L. Johnson, Andreas Galler, Tae Wu Kim, Jong Goo Kim, Deokbeom Suh, Jiwon Moon, Joonghan Kim, Kiryong Hong, Laurent Guérin, Tae Kyu Kim, Michael Wulff, Christian Bressler, Hyotcherl Ihee

Research output: Contribution to journalArticle

8 Citations (Scopus)

Abstract

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 CHI2 radical, the CHI2-I isomer, and the CHI2+ ion, is the dominant intermediate species formed in the photolysis of iodoform (CHI3)? Herein, by combining time-resolved X-ray liquidography (TRXL) and time-resolved X-ray absorption spectroscopy (TR-XAS), we present strong evidence that the CHI2 radical is dominantly formed from the photolysis of CHI3 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 CHI2-I isomer within our signal-to-noise ratio, indicating that, if formed, the CHI2-I isomer must be a minor intermediate. The TR-XAS transient spectra measured at the iodine L1 and L3 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.

Original languageEnglish
Pages (from-to)23298-23302
Number of pages5
JournalPhysical Chemistry Chemical Physics
Volume17
Issue number36
DOIs
Publication statusPublished - 2015 Aug 14

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X ray absorption spectroscopy
absorption spectroscopy
Isomers
Scattering
X rays
Photolysis
scattering
x rays
isomers
Iodine
Methanol
Signal to noise ratio
photolysis
Ions
slicing
iodine
signal to noise ratios
methyl alcohol

All Science Journal Classification (ASJC) codes

  • Physics and Astronomy(all)
  • Physical and Theoretical Chemistry

Cite this

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, Jiwon ; Kim, Joonghan ; Hong, Kiryong ; Guérin, Laurent ; Kim, Tae Kyu ; Wulff, Michael ; Bressler, Christian ; Ihee, Hyotcherl. / Identifying the major intermediate species by combining time-resolved X-ray solution scattering and X-ray absorption spectroscopy. In: Physical Chemistry Chemical Physics. 2015 ; Vol. 17, No. 36. pp. 23298-23302.
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abstract = "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 CHI2 radical, the CHI2-I isomer, and the CHI2+ ion, is the dominant intermediate species formed in the photolysis of iodoform (CHI3)? Herein, by combining time-resolved X-ray liquidography (TRXL) and time-resolved X-ray absorption spectroscopy (TR-XAS), we present strong evidence that the CHI2 radical is dominantly formed from the photolysis of CHI3 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 CHI2-I isomer within our signal-to-noise ratio, indicating that, if formed, the CHI2-I isomer must be a minor intermediate. The TR-XAS transient spectra measured at the iodine L1 and L3 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.",
author = "Kim, {Kyung Hwan} and Jeongho Kim and Oang, {Key Young} and Lee, {Jae Hyuk} and Daniel Grolimund and Milne, {Christopher J.} and Penfold, {Thomas J.} and Johnson, {Steven L.} and Andreas Galler and Kim, {Tae Wu} and Kim, {Jong Goo} and Deokbeom Suh and Jiwon Moon and Joonghan Kim and Kiryong Hong and Laurent Gu{\'e}rin and Kim, {Tae Kyu} and Michael Wulff and Christian Bressler and Hyotcherl Ihee",
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Kim, KH, Kim, J, Oang, KY, Lee, JH, Grolimund, D, Milne, CJ, Penfold, TJ, Johnson, SL, Galler, A, Kim, TW, Kim, JG, Suh, D, Moon, J, Kim, J, Hong, K, Guérin, L, Kim, TK, Wulff, M, Bressler, C & Ihee, H 2015, 'Identifying the major intermediate species by combining time-resolved X-ray solution scattering and X-ray absorption spectroscopy', Physical Chemistry Chemical Physics, vol. 17, no. 36, pp. 23298-23302. https://doi.org/10.1039/c5cp03686k

Identifying the major intermediate species by combining time-resolved X-ray solution scattering and X-ray absorption spectroscopy. / 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, Jiwon; Kim, Joonghan; Hong, Kiryong; Guérin, Laurent; Kim, Tae Kyu; Wulff, Michael; Bressler, Christian; Ihee, Hyotcherl.

In: Physical Chemistry Chemical Physics, Vol. 17, No. 36, 14.08.2015, p. 23298-23302.

Research output: Contribution to journalArticle

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T1 - Identifying the major intermediate species by combining time-resolved X-ray solution scattering and X-ray absorption spectroscopy

AU - Kim, Kyung Hwan

AU - Kim, Jeongho

AU - Oang, Key Young

AU - Lee, Jae Hyuk

AU - Grolimund, Daniel

AU - Milne, Christopher J.

AU - Penfold, Thomas J.

AU - Johnson, Steven L.

AU - Galler, Andreas

AU - Kim, Tae Wu

AU - Kim, Jong Goo

AU - Suh, Deokbeom

AU - Moon, Jiwon

AU - Kim, Joonghan

AU - Hong, Kiryong

AU - Guérin, Laurent

AU - Kim, Tae Kyu

AU - Wulff, Michael

AU - Bressler, Christian

AU - Ihee, Hyotcherl

PY - 2015/8/14

Y1 - 2015/8/14

N2 - 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 CHI2 radical, the CHI2-I isomer, and the CHI2+ ion, is the dominant intermediate species formed in the photolysis of iodoform (CHI3)? Herein, by combining time-resolved X-ray liquidography (TRXL) and time-resolved X-ray absorption spectroscopy (TR-XAS), we present strong evidence that the CHI2 radical is dominantly formed from the photolysis of CHI3 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 CHI2-I isomer within our signal-to-noise ratio, indicating that, if formed, the CHI2-I isomer must be a minor intermediate. The TR-XAS transient spectra measured at the iodine L1 and L3 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.

AB - 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 CHI2 radical, the CHI2-I isomer, and the CHI2+ ion, is the dominant intermediate species formed in the photolysis of iodoform (CHI3)? Herein, by combining time-resolved X-ray liquidography (TRXL) and time-resolved X-ray absorption spectroscopy (TR-XAS), we present strong evidence that the CHI2 radical is dominantly formed from the photolysis of CHI3 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 CHI2-I isomer within our signal-to-noise ratio, indicating that, if formed, the CHI2-I isomer must be a minor intermediate. The TR-XAS transient spectra measured at the iodine L1 and L3 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.

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