Chemistry

Ultrafast X-ray diffraction of transient molecular structures in solution

H. Ihee, M. Lorenc, Tae Kyu Kim, Q. Y. Kong, M. Cammarata, J. H. Lee, S. Bratos, M. Wulff

Research output: Contribution to journalArticle

167 Citations (Scopus)

Abstract

We report direct structural evidence of the bridged radical (CH 2ICH2•) in a polar solution, obtained using time-resolved liquid-phase x-ray diffraction. This transient intermediate has long been hypothesized to explain stereochemical control in many association and/or dissociation reactions involving haloalkanes. Ultrashort optical pulses were used to dissociate an iodine atom from the haloethane molecule (C 2H4I2) dissolved in methanol, and the diffraction of picosecond x-ray pulses from a synchrotron supports the following structural dynamics, with ∼0.01 angstrom spatial resolution and ∼100 picosecond time resolution: The loss of one iodine atom from C2H 4I2 leads to the C-I-C triangular geometry of CH 2ICH2•. This transient C2H4I then binds to an iodine atom to form a new species, the C2H 4I-I isomer, which eventually decays into C2H4 + I2. Solvent dynamics were also extracted from the data, revealing a change in the solvent cage geometry, heating, and thermal expansion.

Original languageEnglish
Pages (from-to)1223-1227
Number of pages5
JournalScience
Volume309
Issue number5738
DOIs
Publication statusPublished - 2005 Aug 19

Fingerprint

Molecular Structure
X-Ray Diffraction
Iodine
X-Rays
Synchrotrons
Heating
Methanol
Hot Temperature

All Science Journal Classification (ASJC) codes

  • General

Cite this

Ihee, H., Lorenc, M., Kim, T. K., Kong, Q. Y., Cammarata, M., Lee, J. H., ... Wulff, M. (2005). Chemistry: Ultrafast X-ray diffraction of transient molecular structures in solution. Science, 309(5738), 1223-1227. https://doi.org/10.1126/science.1114782
Ihee, H. ; Lorenc, M. ; Kim, Tae Kyu ; Kong, Q. Y. ; Cammarata, M. ; Lee, J. H. ; Bratos, S. ; Wulff, M. / Chemistry : Ultrafast X-ray diffraction of transient molecular structures in solution. In: Science. 2005 ; Vol. 309, No. 5738. pp. 1223-1227.
@article{c38bf64fee7140718d8ebc0cc98b5008,
title = "Chemistry: Ultrafast X-ray diffraction of transient molecular structures in solution",
abstract = "We report direct structural evidence of the bridged radical (CH 2ICH2•) in a polar solution, obtained using time-resolved liquid-phase x-ray diffraction. This transient intermediate has long been hypothesized to explain stereochemical control in many association and/or dissociation reactions involving haloalkanes. Ultrashort optical pulses were used to dissociate an iodine atom from the haloethane molecule (C 2H4I2) dissolved in methanol, and the diffraction of picosecond x-ray pulses from a synchrotron supports the following structural dynamics, with ∼0.01 angstrom spatial resolution and ∼100 picosecond time resolution: The loss of one iodine atom from C2H 4I2 leads to the C-I-C triangular geometry of CH 2ICH2•. This transient C2H4I then binds to an iodine atom to form a new species, the C2H 4I-I isomer, which eventually decays into C2H4 + I2. Solvent dynamics were also extracted from the data, revealing a change in the solvent cage geometry, heating, and thermal expansion.",
author = "H. Ihee and M. Lorenc and Kim, {Tae Kyu} and Kong, {Q. Y.} and M. Cammarata and Lee, {J. H.} and S. Bratos and M. Wulff",
year = "2005",
month = "8",
day = "19",
doi = "10.1126/science.1114782",
language = "English",
volume = "309",
pages = "1223--1227",
journal = "Science",
issn = "0036-8075",
publisher = "American Association for the Advancement of Science",
number = "5738",

}

Ihee, H, Lorenc, M, Kim, TK, Kong, QY, Cammarata, M, Lee, JH, Bratos, S & Wulff, M 2005, 'Chemistry: Ultrafast X-ray diffraction of transient molecular structures in solution', Science, vol. 309, no. 5738, pp. 1223-1227. https://doi.org/10.1126/science.1114782

Chemistry : Ultrafast X-ray diffraction of transient molecular structures in solution. / Ihee, H.; Lorenc, M.; Kim, Tae Kyu; Kong, Q. Y.; Cammarata, M.; Lee, J. H.; Bratos, S.; Wulff, M.

In: Science, Vol. 309, No. 5738, 19.08.2005, p. 1223-1227.

Research output: Contribution to journalArticle

TY - JOUR

T1 - Chemistry

T2 - Ultrafast X-ray diffraction of transient molecular structures in solution

AU - Ihee, H.

AU - Lorenc, M.

AU - Kim, Tae Kyu

AU - Kong, Q. Y.

AU - Cammarata, M.

AU - Lee, J. H.

AU - Bratos, S.

AU - Wulff, M.

PY - 2005/8/19

Y1 - 2005/8/19

N2 - We report direct structural evidence of the bridged radical (CH 2ICH2•) in a polar solution, obtained using time-resolved liquid-phase x-ray diffraction. This transient intermediate has long been hypothesized to explain stereochemical control in many association and/or dissociation reactions involving haloalkanes. Ultrashort optical pulses were used to dissociate an iodine atom from the haloethane molecule (C 2H4I2) dissolved in methanol, and the diffraction of picosecond x-ray pulses from a synchrotron supports the following structural dynamics, with ∼0.01 angstrom spatial resolution and ∼100 picosecond time resolution: The loss of one iodine atom from C2H 4I2 leads to the C-I-C triangular geometry of CH 2ICH2•. This transient C2H4I then binds to an iodine atom to form a new species, the C2H 4I-I isomer, which eventually decays into C2H4 + I2. Solvent dynamics were also extracted from the data, revealing a change in the solvent cage geometry, heating, and thermal expansion.

AB - We report direct structural evidence of the bridged radical (CH 2ICH2•) in a polar solution, obtained using time-resolved liquid-phase x-ray diffraction. This transient intermediate has long been hypothesized to explain stereochemical control in many association and/or dissociation reactions involving haloalkanes. Ultrashort optical pulses were used to dissociate an iodine atom from the haloethane molecule (C 2H4I2) dissolved in methanol, and the diffraction of picosecond x-ray pulses from a synchrotron supports the following structural dynamics, with ∼0.01 angstrom spatial resolution and ∼100 picosecond time resolution: The loss of one iodine atom from C2H 4I2 leads to the C-I-C triangular geometry of CH 2ICH2•. This transient C2H4I then binds to an iodine atom to form a new species, the C2H 4I-I isomer, which eventually decays into C2H4 + I2. Solvent dynamics were also extracted from the data, revealing a change in the solvent cage geometry, heating, and thermal expansion.

UR - http://www.scopus.com/inward/record.url?scp=23844525079&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=23844525079&partnerID=8YFLogxK

U2 - 10.1126/science.1114782

DO - 10.1126/science.1114782

M3 - Article

VL - 309

SP - 1223

EP - 1227

JO - Science

JF - Science

SN - 0036-8075

IS - 5738

ER -