skip to main content
DOE PAGES title logo U.S. Department of Energy
Office of Scientific and Technical Information

Title: Solvent-dependent complex reaction pathways of bromoform revealed by time-resolved X-ray solution scattering and X-ray transient absorption spectroscopy

Abstract

The photochemical reaction pathways of CHBr3 in solution were unveiled using two complementary X-ray techniques, time-resolved X-ray solution scattering (TRXSS) and X-ray transient absorption spectroscopy, in a wide temporal range from 100 ps to tens of microseconds. By performing comparative measurements in protic (methanol) and aprotic (methylcyclohexane) solvents, we found that the reaction pathways depend significantly on the solvent properties. In methanol, the major photoproducts are CH3OCHBr2 and HBr generated by rapid solvolysis of iso-CHBr2-Br, an isomer of CHBr3. In contrast, in methylcyclohexane, iso-CHBr2-Br returns to CHBr3 without solvolysis. In both solvents, the formation of CHBr2 and Br is a competing reaction channel. From the structural analysis of TRXSS data, we determined the structures of key intermediate species, CH3OCHBr2 and iso-CHBr2-Br in methanol and methylcyclohexane, respectively, which are consistent with the structures from density functional theory calculations.

Authors:
 [1];  [2];  [3];  [4];  [3]; ORCiD logo [5];  [6];  [7];  [7]; ORCiD logo [7];  [8];  [3];  [3];  [3];  [9]; ORCiD logo [10]; ORCiD logo [7]
+ Show Author Affiliations
  1. Synchrotron Soleil, Gif-sur-Yvette (France); Liaocheng Univ. (China)
  2. European XFEL GmbH, Schenefeld (Germany)
  3. Argonne National Lab. (ANL), Argonne, IL (United States)
  4. Pohang Accelerator Lab. (South Korea)
  5. Inha Univ., Incheon (South Korea)
  6. Pohang Univ. of Science and Technology (POSTECH) (South Korea)
  7. Korea Advanced Inst. Science and Technology (KAIST), Daejeon (South Korea); Inst. for Basic Science (IBS), Daejeon (South Korea)
  8. Synchrotron Soleil, Gif-sur-Yvette (France)
  9. Argonne National Lab. (ANL), Argonne, IL (United States); Northwestern Univ., Evanston, IL (United States)
  10. European Synchrotron Radiation Facility (ESRF), Grenoble (France)
Publication Date:
Research Org.:
Argonne National Lab. (ANL), Argonne, IL (United States)
Sponsoring Org.:
Institute for Basic Science; USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences & Biosciences Division
OSTI Identifier:
1607391
Alternate Identifier(s):
OSTI ID: 1580301
Grant/Contract Number:  
AC02-06CH11357
Resource Type:
Accepted Manuscript
Journal Name:
Structural Dynamics
Additional Journal Information:
Journal Volume: 6; Journal Issue: 6; Conference: 5.International Conference on Ultrafast Structural Dynamics (ICUSD), Daejeon (South Korea), 25-28 Jun 2019; Journal ID: ISSN 2329-7778
Publisher:
American Crystallographic Association/AIP
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; X-ray absorption; X-ray scattering; Bond dissociation; Photochemistry; Reaction dynamics; Ultrafast spectroscopy; Isomerism; Photochemical reactions; Atmospheric chemistry; Transient-absorption spectroscopy; Density functional theory; Reaction mechanisms; Time resolved X-ray spectroscopy

Citation Formats

Kong, Qingyu, Khakhulin, Dmitry, Shkrob, Ilya A., Lee, Jae Hyuk, Zhang, Xiaoyi, Kim, Jeongho, Kim, Kyung Hwan, Jo, Junbeom, Kim, Jungmin, Kang, Jaedong, Pham, Van-Thai, Jennings, Guy, Kurtz, Charles, Spence, Rick, Chen, Lin X., Wulff, Michael, and Ihee, Hyotcherl. Solvent-dependent complex reaction pathways of bromoform revealed by time-resolved X-ray solution scattering and X-ray transient absorption spectroscopy. United States: N. p., 2019. Web. doi:10.1063/1.5132968.
Copy to clipboard
Kong, Qingyu, Khakhulin, Dmitry, Shkrob, Ilya A., Lee, Jae Hyuk, Zhang, Xiaoyi, Kim, Jeongho, Kim, Kyung Hwan, Jo, Junbeom, Kim, Jungmin, Kang, Jaedong, Pham, Van-Thai, Jennings, Guy, Kurtz, Charles, Spence, Rick, Chen, Lin X., Wulff, Michael, & Ihee, Hyotcherl. Solvent-dependent complex reaction pathways of bromoform revealed by time-resolved X-ray solution scattering and X-ray transient absorption spectroscopy. United States. doi:10.1063/1.5132968.
Copy to clipboard
Kong, Qingyu, Khakhulin, Dmitry, Shkrob, Ilya A., Lee, Jae Hyuk, Zhang, Xiaoyi, Kim, Jeongho, Kim, Kyung Hwan, Jo, Junbeom, Kim, Jungmin, Kang, Jaedong, Pham, Van-Thai, Jennings, Guy, Kurtz, Charles, Spence, Rick, Chen, Lin X., Wulff, Michael, and Ihee, Hyotcherl. Tue . "Solvent-dependent complex reaction pathways of bromoform revealed by time-resolved X-ray solution scattering and X-ray transient absorption spectroscopy". United States. doi:10.1063/1.5132968. https://www.osti.gov/servlets/purl/1607391.
Copy to clipboard
@article{osti_1607391,
title = {Solvent-dependent complex reaction pathways of bromoform revealed by time-resolved X-ray solution scattering and X-ray transient absorption spectroscopy},
author = {Kong, Qingyu and Khakhulin, Dmitry and Shkrob, Ilya A. and Lee, Jae Hyuk and Zhang, Xiaoyi and Kim, Jeongho and Kim, Kyung Hwan and Jo, Junbeom and Kim, Jungmin and Kang, Jaedong and Pham, Van-Thai and Jennings, Guy and Kurtz, Charles and Spence, Rick and Chen, Lin X. and Wulff, Michael and Ihee, Hyotcherl},
abstractNote = {The photochemical reaction pathways of CHBr3 in solution were unveiled using two complementary X-ray techniques, time-resolved X-ray solution scattering (TRXSS) and X-ray transient absorption spectroscopy, in a wide temporal range from 100 ps to tens of microseconds. By performing comparative measurements in protic (methanol) and aprotic (methylcyclohexane) solvents, we found that the reaction pathways depend significantly on the solvent properties. In methanol, the major photoproducts are CH3OCHBr2 and HBr generated by rapid solvolysis of iso-CHBr2-Br, an isomer of CHBr3. In contrast, in methylcyclohexane, iso-CHBr2-Br returns to CHBr3 without solvolysis. In both solvents, the formation of CHBr2 and Br is a competing reaction channel. From the structural analysis of TRXSS data, we determined the structures of key intermediate species, CH3OCHBr2 and iso-CHBr2-Br in methanol and methylcyclohexane, respectively, which are consistent with the structures from density functional theory calculations.},
doi = {10.1063/1.5132968},
journal = {Structural Dynamics},
number = 6,
volume = 6,
place = {United States},
year = {2019},
month = {12}
}
Copy to clipboard
Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record
DOI:  10.1063/1.5132968
Copyright Statement
Other availability
Search WorldCat Search WorldCat to find libraries that may hold this journal
Citation Metrics:
Cited by: 1 work
Citation information provided by
Web of Science
Save / Share:
Export Metadata
Save to My Library
You must Sign In or Create an Account in order to save documents to your library.

Works referenced in this record:

Photochemical Reaction Pathways of Carbon Tetrabromide in Solution Probed by Picosecond X-ray Diffraction
journal, November 2007

  • Kong, Qingyu; Wulff, Michael; Lee, Jae Hyuk
  • Journal of the American Chemical Society, Vol. 129, Issue 44
  • DOI: 10.1021/ja073503e

Water-Catalyzed Dehalogenation Reactions of Isobromoform and Its Reaction Products
journal, March 2004

  • Kwok, Wai Ming; Zhao, Cunyuan; Li, Yun-Liang
  • Journal of the American Chemical Society, Vol. 126, Issue 10
  • DOI: 10.1021/ja0390552

Structural Determination of a Transient Isomer of CH 2 I 2 by Picosecond X-Ray Diffraction
journal, June 2005

Ultraviolet photodissociation of bromoform at 234 and 267 nm by means of ion velocity imaging
journal, August 2002

  • Xu, Dadong; Francisco, Joseph S.; Huang, Jianhua
  • The Journal of Chemical Physics, Vol. 117, Issue 6
  • DOI: 10.1063/1.1491877

Solvent-dependent structure of molecular iodine probed by picosecond X-ray solution scattering
journal, January 2015

  • Kim, Kyung Hwan; Ki, Hosung; Lee, Jae Hyuk
  • Physical Chemistry Chemical Physics, Vol. 17, Issue 14
  • DOI: 10.1039/C5CP00536A

Visualizing Solution-Phase Reaction Dynamics with Time-Resolved X-ray Liquidography
journal, February 2009

  • Ihee, Hyotcherl
  • Accounts of Chemical Research, Vol. 42, Issue 2
  • DOI: 10.1021/ar800168v

Identifying the major intermediate species by combining time-resolved X-ray solution scattering and X-ray absorption spectroscopy
journal, January 2015

  • Kim, Kyung Hwan; Kim, Jeongho; Oang, Key Young
  • Physical Chemistry Chemical Physics, Vol. 17, Issue 36
  • DOI: 10.1039/C5CP03686K

Photolysis of Br 2 in CCl 4 studied by time-resolved X-ray scattering
journal, February 2010

  • Kong, Qingyu; Lee, Jae Hyuk; Lo Russo, Manuela
  • Acta Crystallographica Section A Foundations of Crystallography, Vol. 66, Issue 2
  • DOI: 10.1107/S0108767309054993

Structural Dynamics of Bismuth Triiodide in Solution Triggered by Photoinduced Ligand-to-Metal Charge Transfer
journal, February 2019

  • Choi, Eun Hyuk; Ahn, Doo-Sik; Park, Sungjun
  • The Journal of Physical Chemistry Letters, Vol. 10, Issue 6
  • DOI: 10.1021/acs.jpclett.9b00365

Transient resonance Raman investigation of CHBr2 and CHBrCl radicals
journal, October 2002

Ultrafast Observation of Isomerization and Complexation in the Photolysis of Bromoform in Solution †
journal, January 2010

  • Carrier, Stacey L.; Preston, Thomas J.; Dutta, Maitreya
  • The Journal of Physical Chemistry A, Vol. 114, Issue 3
  • DOI: 10.1021/jp908725t

Filming the Birth of Molecules and Accompanying Solvent Rearrangement
journal, February 2013

  • Lee, Jae Hyuk; Wulff, Michael; Bratos, Savo
  • Journal of the American Chemical Society, Vol. 135, Issue 8
  • DOI: 10.1021/ja312513w

Highly Accurate Excited-State Structure of [Os(bpy) 2 dcbpy] 2+ Determined by X-ray Transient Absorption Spectroscopy
journal, June 2014

  • Zhang, Xiaoyi; Canton, Sophie E.; Smolentsev, Grigory
  • Journal of the American Chemical Society, Vol. 136, Issue 24
  • DOI: 10.1021/ja5040733

Visualizing the non-equilibrium dynamics of photoinduced intramolecular electron transfer with femtosecond X-ray pulses
journal, March 2015

  • Canton, Sophie E.; Kjær, Kasper S.; Vankó, György
  • Nature Communications, Vol. 6, Issue 1
  • DOI: 10.1038/ncomms7359

Ultrafast X-Ray Scattering Measurements of Coherent Structural Dynamics on the Ground-State Potential Energy Surface of a Diplatinum Molecule
journal, February 2019

Spatiotemporal Kinetics in Solution Studied by Time-Resolved X-Ray Liquidography (Solution Scattering)
journal, August 2009

Brominations with N -Bromosuccinimide and Related Compounds. The Wohl-Ziegler Reaction.
journal, October 1948

A neutron diffraction study of dimethyl sulphoxide–water mixtures
journal, July 1992

  • Soper, A. K.; Luzar, Alenka
  • The Journal of Chemical Physics, Vol. 97, Issue 2
  • DOI: 10.1063/1.463259

Capturing Transient Structures in the Elimination Reaction of Haloalkane in Solution by Transient X-ray Diffraction
journal, May 2008

  • Lee, Jae Hyuk; Kim, Tae Kyu; Kim, Joonghan
  • Journal of the American Chemical Society, Vol. 130, Issue 18
  • DOI: 10.1021/ja710267u

Direct Observation of a Transiently Formed Isomer During Iodoform Photolysis in Solution by Time-Resolved X-ray Liquidography
journal, January 2018

Ultrafast X-ray Solution Scattering Reveals Different Reaction Pathways in the Photolysis of Triruthenium Dodecacarbonyl (Ru 3 (CO) 12 ) after Ultraviolet and Visible Excitation
journal, March 2010

  • Kong, Qingyu; Lee, Jae Hyuk; Kim, Kyung Hwan
  • Journal of the American Chemical Society, Vol. 132, Issue 8
  • DOI: 10.1021/ja9097548

Volume-conserving trans–cis isomerization pathways in photoactive yellow protein visualized by picosecond X-ray crystallography
journal, February 2013

  • Jung, Yang Ouk; Lee, Jae Hyuk; Kim, Joonghan
  • Nature Chemistry, Vol. 5, Issue 3
  • DOI: 10.1038/nchem.1565

Atomistic characterization of the active-site solvation dynamics of a model photocatalyst
journal, November 2016

  • van Driel, Tim B.; Kjær, Kasper S.; Hartsock, Robert W.
  • Nature Communications, Vol. 7, Issue 1
  • DOI: 10.1038/ncomms13678

Protein Structural Dynamics of Photoactive Yellow Protein in Solution Revealed by Pump–Probe X-ray Solution Scattering
journal, February 2012

  • Kim, Tae Wu; Lee, Jae Hyuk; Choi, Jungkweon
  • Journal of the American Chemical Society, Vol. 134, Issue 6
  • DOI: 10.1021/ja210435n

Ultrafast X-ray Diffraction of Transient Molecular Structures in Solution
journal, August 2005

Protein Structural Dynamics Revealed by Time-Resolved X-ray Solution Scattering
journal, July 2015

Initial metal–metal bond breakage detected by fs X-ray scattering in the photolysis of Ru 3 (CO) 12 in cyclohexane at 400 nm
journal, January 2019

  • Kong, Q. Y.; Laursen, M. G.; Haldrup, K.
  • Photochemical & Photobiological Sciences, Vol. 18, Issue 2
  • DOI: 10.1039/C8PP00420J

Photodissociation of Bromoform at 248 nm:  Single and Multiphoton Processes
journal, March 2004

  • Zou, Peng; Shu, Jinian; Sears, Trevor J.
  • The Journal of Physical Chemistry A, Vol. 108, Issue 9
  • DOI: 10.1021/jp0310394

Atmospheric chemistry of CH2BR2: Rate coefficients for its reaction with Cl atoms and OH and the chemistry of the CHBr2O radical
journal, January 1996

X-ray snapshots reveal conformational influence on active site ligation during metalloprotein folding
journal, January 2019

  • Hsu, Darren J.; Leshchev, Denis; Rimmerman, Dolev
  • Chemical Science, Vol. 10, Issue 42
  • DOI: 10.1039/C9SC02630D

Time-Resolved X-ray Scattering of an Electronically Excited State in Solution. Structure of the 3 A 2u State of Tetrakis-μ-pyrophosphitodiplatinate(II)
journal, January 2009

  • Christensen, Morten; Haldrup, Kristoffer; Bechgaard, Klaus
  • Journal of the American Chemical Society, Vol. 131, Issue 2
  • DOI: 10.1021/ja804485d

Global sampling of the photochemical reaction paths of bromoform by ultrafast deep-UV through near-IR transient absorption and ab initio multiconfigurational calculations
journal, March 2013

  • Pal, S. K.; Mereshchenko, A. S.; Butaeva, E. V.
  • The Journal of Chemical Physics, Vol. 138, Issue 12
  • DOI: 10.1063/1.4789268

State-Resolved Dynamics of the CH(A 2 Δ) Channels from Single and Multiple Photon Dissociation of Bromoform in the 10−20 eV Energy Range †
journal, March 2006

  • Chikan, Viktor; Fournier, Frederic; Leone, Stephen R.
  • The Journal of Physical Chemistry A, Vol. 110, Issue 9
  • DOI: 10.1021/jp0538013

Ultrafast X-Ray Solution Scattering Reveals an Unknown Reaction Intermediate in the Photolysis of [Ru 3 (CO) 12 ]
journal, June 2008

  • Kong, Qingyu; Lee, Jae Hyuk; Plech, Anton
  • Angewandte Chemie International Edition, Vol. 47, Issue 30
  • DOI: 10.1002/anie.200801153

Finding intersections between electronic excited state potential energy surfaces with simultaneous ultrafast X-ray scattering and spectroscopy
journal, January 2019

  • Kjær, Kasper S.; Van Driel, Tim B.; Harlang, Tobias C. B.
  • Chemical Science, Vol. 10, Issue 22
  • DOI: 10.1039/C8SC04023K

Transient isomers in the photodissociation of bromoiodomethane
journal, April 2018

  • Marcellini, Moreno; Nasedkin, Alexandr; Zietz, Burkhard
  • The Journal of Chemical Physics, Vol. 148, Issue 13
  • DOI: 10.1063/1.5005595

Resonance Raman investigation of the short-time dynamics of the ultraviolet photodissociation of bromoform
journal, August 2002

Direct observation of bond formation in solution with femtosecond X-ray scattering
journal, February 2015

  • Kim, Kyung Hwan; Kim, Jong Goo; Nozawa, Shunsuke
  • Nature, Vol. 518, Issue 7539
  • DOI: 10.1038/nature14163

Visualizing Chemical Reactions in Solution by Picosecond X-Ray Diffraction
journal, March 2004

Solvent-Dependent Molecular Structure of Ionic Species Directly Measured by Ultrafast X-Ray Solution Scattering
journal, April 2013

Transient x-ray absorption spectroscopy of hydrated halogen atom
journal, February 2008

  • Elles, Christopher G.; Shkrob, Ilya A.; Crowell, Robert A.
  • The Journal of Chemical Physics, Vol. 128, Issue 6
  • DOI: 10.1063/1.2827456

Rotational dephasing of a gold complex probed by anisotropic femtosecond x-ray solution scattering using an x-ray free-electron laser
journal, November 2015

  • Kim, Jong Goo; Kim, Kyung Hwan; Oang, Key Young
  • Journal of Physics B: Atomic, Molecular and Optical Physics, Vol. 48, Issue 24
  • DOI: 10.1088/0953-4075/48/24/244005

Ultrafast X-ray Absorption Spectroscopy
journal, April 2004

  • Bressler, Christian; Chergui, Majed
  • Chemical Reviews, Vol. 104, Issue 4
  • DOI: 10.1021/cr0206667

Cooperative protein structural dynamics of homodimeric hemoglobin linked to water cluster at subunit interface revealed by time-resolved X-ray solution scattering
journal, March 2016

  • Kim, Jong Goo; Muniyappan, Srinivasan; Oang, Key Young
  • Structural Dynamics, Vol. 3, Issue 2
  • DOI: 10.1063/1.4947071

Tracking the structural dynamics of proteins in solution using time-resolved wide-angle X-ray scattering
journal, September 2008

  • Cammarata, Marco; Levantino, Matteo; Schotte, Friedrich
  • Nature Methods, Vol. 5, Issue 10
  • DOI: 10.1038/nmeth.1255

Tracking reaction dynamics in solution by pump–probe X-ray absorption spectroscopy and X-ray liquidography (solution scattering)
journal, January 2016

  • Kim, Jeongho; Kim, Kyung Hwan; Oang, Key Young
  • Chemical Communications, Vol. 52, Issue 19
  • DOI: 10.1039/C5CC08949B

Photochemical Processes Revealed by X-ray Transient Absorption Spectroscopy
journal, November 2013

  • Chen, Lin X.; Zhang, Xiaoyi
  • The Journal of Physical Chemistry Letters, Vol. 4, Issue 22
  • DOI: 10.1021/jz401750g

Roaming-mediated ultrafast isomerization of geminal tri-bromides in the gas and liquid phases
journal, June 2015

  • Mereshchenko, Andrey S.; Butaeva, Evgeniia V.; Borin, Veniamin A.
  • Nature Chemistry, Vol. 7, Issue 7
  • DOI: 10.1038/nchem.2278

Structural Tracking of a Bimolecular Reaction in Solution by Time-Resolved X-Ray Scattering
journal, May 2009

  • Haldrup, Kristoffer; Christensen, Morten; Cammarata, Marco
  • Angewandte Chemie International Edition, Vol. 48, Issue 23
  • DOI: 10.1002/anie.200900741

Transient X-ray Diffraction Reveals Global and Major Reaction Pathways for the Photolysis of Iodoform in Solution
journal, January 2008

  • Lee, Jae Hyuk; Kim, Joonghan; Cammarata, Marco
  • Angewandte Chemie International Edition, Vol. 47, Issue 6
  • DOI: 10.1002/anie.200704150

The Role of Br2 and BrCl in Surface Ozone Destruction at Polar Sunrise
journal, January 2001

Global Reaction Pathways in the Photodissociation of I 3 − Ions in Solution at 267 and 400 nm Studied by Picosecond X-ray Liquidography
journal, October 2013

Femtosecond X-Ray Scattering Study of Ultrafast Photoinduced Structural Dynamics in Solvated [ Co ( terpy ) 2 ] 2 +
journal, June 2016

Femtosecond X-ray solution scattering reveals that bond formation mechanism of a gold trimer complex is independent of excitation wavelength
journal, April 2016

  • Kim, Kyung Hwan; Kim, Jong Goo; Oang, Key Young
  • Structural Dynamics, Vol. 3, Issue 4
  • DOI: 10.1063/1.4948516

Chromophore-Removal-Induced Conformational Change in Photoactive Yellow Protein Determined through Spectroscopic and X-ray Solution Scattering Studies
journal, April 2018

  • Kim, Youngmin; Ganesan, Prabhakar; Jo, Junbeom
  • The Journal of Physical Chemistry B, Vol. 122, Issue 16
  • DOI: 10.1021/acs.jpcb.8b01768
    [ × clear filter / sort ]

    Similar Records in DOE PAGES and OSTI.GOV collections: