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Title: Deuterium isotope effects in polymerization of benzene under pressure

Abstract

The enormous versatility in the properties of carbon materials depends on the content of the sp2 and sp3 covalent bonds. Under compression, if intermolecular distances cross a critical threshold, then unsaturated hydrocarbons gradually transform to saturated carbon polymers. However, the mechanism of polymerization, even for benzene, the simplest aromatic hydrocarbon, is still not understood. We used high-pressure synchrotron X-ray, neutron diffraction, and micro-Raman spectroscopy together with density functional calculations to investigate the isotope effects in benzene isotopologues C6H6 and C6D6 up to 46.0 GPa. Raman spectra of polymeric products recovered from comparable pressures show the progression of polymerization exhibiting a pronounced kinetic isotope effect. Kinetically retarded reactions in C6D6 shed light on the mechanism of polymerization of benzene. Lastly, we find that C6D6-derived products recovered from P < 35 GPa actively react with moisture, forming polymers with higher sp3 hydrogen contents. Significant isotopic shift (≥7 GPa) in persistence of Bragg reflections of C6D6 is observed.

Authors:
ORCiD logo [1];  [1]; ORCiD logo [2];  [1];  [1];  [1];  [3];  [3];  [4]; ORCiD logo [1]
+ Show Author Affiliations
  1. Univ. of Utah, Salt Lake City, UT (United States)
  2. Northwestern Univ., Evanston, IL (United States)
  3. Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
  4. Carnegie Institute of Washington, Argonne, IL (United States)
Publication Date:
Research Org.:
Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Spallation Neutron Source (SNS)
Sponsoring Org.:
USDOE
OSTI Identifier:
1366413
Grant/Contract Number:  
AC05-00OR22725
Resource Type:
Accepted Manuscript
Journal Name:
Journal of Physical Chemistry Letters
Additional Journal Information:
Journal Volume: 8; Journal Issue: 8; Journal ID: ISSN 1948-7185
Publisher:
American Chemical Society
Country of Publication:
United States
Language:
English
Subject:
36 MATERIALS SCIENCE; 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats

Cai, Weizhao, Dunuwille, Mihindra, He, Jiangang, Taylor, Trevor V., Hinton, Jasmine K., MacLean, Mary C., Molaison, Jamie J., dos Santos, Antonio M., Sinogeikin, Stanislav, and Deemyad, Shanti. Deuterium isotope effects in polymerization of benzene under pressure. United States: N. p., 2017. Web. doi:10.1021/acs.jpclett.7b00536.
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Cai, Weizhao, Dunuwille, Mihindra, He, Jiangang, Taylor, Trevor V., Hinton, Jasmine K., MacLean, Mary C., Molaison, Jamie J., dos Santos, Antonio M., Sinogeikin, Stanislav, & Deemyad, Shanti. Deuterium isotope effects in polymerization of benzene under pressure. United States. https://doi.org/10.1021/acs.jpclett.7b00536
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Cai, Weizhao, Dunuwille, Mihindra, He, Jiangang, Taylor, Trevor V., Hinton, Jasmine K., MacLean, Mary C., Molaison, Jamie J., dos Santos, Antonio M., Sinogeikin, Stanislav, and Deemyad, Shanti. Mon . "Deuterium isotope effects in polymerization of benzene under pressure". United States. https://doi.org/10.1021/acs.jpclett.7b00536. https://www.osti.gov/servlets/purl/1366413.
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@article{osti_1366413,
title = {Deuterium isotope effects in polymerization of benzene under pressure},
author = {Cai, Weizhao and Dunuwille, Mihindra and He, Jiangang and Taylor, Trevor V. and Hinton, Jasmine K. and MacLean, Mary C. and Molaison, Jamie J. and dos Santos, Antonio M. and Sinogeikin, Stanislav and Deemyad, Shanti},
abstractNote = {The enormous versatility in the properties of carbon materials depends on the content of the sp2 and sp3 covalent bonds. Under compression, if intermolecular distances cross a critical threshold, then unsaturated hydrocarbons gradually transform to saturated carbon polymers. However, the mechanism of polymerization, even for benzene, the simplest aromatic hydrocarbon, is still not understood. We used high-pressure synchrotron X-ray, neutron diffraction, and micro-Raman spectroscopy together with density functional calculations to investigate the isotope effects in benzene isotopologues C6H6 and C6D6 up to 46.0 GPa. Raman spectra of polymeric products recovered from comparable pressures show the progression of polymerization exhibiting a pronounced kinetic isotope effect. Kinetically retarded reactions in C6D6 shed light on the mechanism of polymerization of benzene. Lastly, we find that C6D6-derived products recovered from P < 35 GPa actively react with moisture, forming polymers with higher sp3 hydrogen contents. Significant isotopic shift (≥7 GPa) in persistence of Bragg reflections of C6D6 is observed.},
doi = {10.1021/acs.jpclett.7b00536},
journal = {Journal of Physical Chemistry Letters},
number = 8,
volume = 8,
place = {United States},
year = {Mon Apr 10 00:00:00 EDT 2017},
month = {Mon Apr 10 00:00:00 EDT 2017}
}
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https://doi.org/10.1021/acs.jpclett.7b00536
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Works referenced in this record:

High-pressure synthesis of crystalline polyethylene using optical catalysis
journal, June 2004

  • Chelazzi, David; Ceppatelli, Matteo; Santoro, Mario
  • Nature Materials, Vol. 3, Issue 7
  • DOI: 10.1038/nmat1147

Bonding Changes in Compressed Superhard Graphite
journal, October 2003

Visible mechanochromic responses of spiropyrans in crystals via pressure-induced isomerization
journal, January 2015

  • Meng, Xiao; Qi, Guangyu; Zhang, Chen
  • Chemical Communications, Vol. 51, Issue 45
  • DOI: 10.1039/C5CC01064K

Benzene-derived carbon nanothreads
journal, September 2014

  • Fitzgibbons, Thomas C.; Guthrie, Malcolm; Xu, En-shi
  • Nature Materials, Vol. 14, Issue 1
  • DOI: 10.1038/nmat4088

First-principles calculation of the mechanical properties of diamond nanothreads
journal, March 2017

Further Rough Compressions to 40,000 Kg/Cm⁲, Especially Certain Liquids
journal, January 1949

  • Bridgman, P. W.
  • Proceedings of the American Academy of Arts and Sciences, Vol. 77, Issue 4
  • DOI: 10.2307/20023533

Backward Stimulated Raman Scattering in Shock-Compressed Benzene
journal, February 1983

In situ Raman spectroscopy of shock-compressed benzene and its derivatives
journal, September 2000

High Pressure Photoinduced Ring Opening of Benzene
journal, February 2002

Exploring Polymorphism: The Case of Benzene
journal, June 2005

  • Raiteri, Paolo; Martoňák, Roman; Parrinello, Michele
  • Angewandte Chemie International Edition, Vol. 44, Issue 24
  • DOI: 10.1002/anie.200462760

Benzene under High Pressure: a Story of Molecular Crystals Transforming to Saturated Networks, with a Possible Intermediate Metallic Phase
journal, June 2011

  • Wen, Xiao-Dong; Hoffmann, Roald; Ashcroft, N. W.
  • Journal of the American Chemical Society, Vol. 133, Issue 23
  • DOI: 10.1021/ja201786y

High-pressure and high-temperature equation of state and phase diagram of solid benzene
journal, September 2005

Association CH···π and No van der Waals Contacts at the Lowest Limits of Crystalline Benzene I and II Stability Regions †
journal, August 2010

  • Katrusiak, Andrzej; Podsiadło, Marcin; Budzianowski, Armand
  • Crystal Growth & Design, Vol. 10, Issue 8
  • DOI: 10.1021/cg1002594

Phase transitions and chemical transformations of benzene up to 550 °C and 30 GPa
journal, November 1993

  • Cansell, François; Fabre, Denise; Petitet, Jean‐Pierre
  • The Journal of Chemical Physics, Vol. 99, Issue 10
  • DOI: 10.1063/1.465711

Phase Transitions and Polymerization of C 6 H 6 –C 6 F 6 Cocrystal under Extreme Conditions
journal, December 2016

  • Wang, Yajie; Wang, Lijuan; Zheng, Haiyan
  • The Journal of Physical Chemistry C, Vol. 120, Issue 51
  • DOI: 10.1021/acs.jpcc.6b11245

Effect of pressure and temperature on the H-atom tunneling in solid phase chemical reactions. The acridine/fluorene system
journal, June 1998

High pressure solid phases of benzene. II. Calculations of the vibration frequencies and evolution of the bonds in C 6 H 6 and C 6 D 6 up to 20 GPa
journal, February 1992

  • Thiéry, M. M.; Besson, J. M.; Bribes, J. L.
  • The Journal of Chemical Physics, Vol. 96, Issue 4
  • DOI: 10.1063/1.462014

Transformation of benzene to a polymer after static pressurization to 30 GPa
journal, June 1990

  • Pruzan, Ph.; Chervin, J. C.; Thiéry, M. M.
  • The Journal of Chemical Physics, Vol. 92, Issue 11
  • DOI: 10.1063/1.458278

Pressure dependence of vibrational modes in solid benzenes C 6 H 6 and C 6 D 6
journal, December 1991

The Deuterium Isotope Effect
journal, August 1955

The Magnitude of the Primary Kinetic Isotope Effect for Compounds of Hydrogen and Deuterium.
journal, June 1961

High pressure solid phases of benzene. I. Raman and x‐ray studies of C 6 H 6 at 294 K up to 25 GPa
journal, October 1988

  • Thiéry, M. M.; Léger, J. M.
  • The Journal of Chemical Physics, Vol. 89, Issue 7
  • DOI: 10.1063/1.454809

Low-pressure phase diagram of crystalline benzene from quantum Monte Carlo
journal, August 2016

  • Azadi, Sam; Cohen, R. E.
  • The Journal of Chemical Physics, Vol. 145, Issue 6
  • DOI: 10.1063/1.4960434

High pressure reactivity of solid benzene probed by infrared spectroscopy
journal, February 2002

  • Ciabini, Lucia; Santoro, Mario; Bini, Roberto
  • The Journal of Chemical Physics, Vol. 116, Issue 7
  • DOI: 10.1063/1.1435570

A comparative analysis of a-C:H by infrared spectroscopy and mass selected thermal effusion
journal, October 1998

  • Ristein, J.; Stief, R. T.; Ley, L.
  • Journal of Applied Physics, Vol. 84, Issue 7
  • DOI: 10.1063/1.368563

High pressure crystal phases of benzene probed by infrared spectroscopy
journal, August 2001

  • Ciabini, Lucia; Santoro, Mario; Bini, Roberto
  • The Journal of Chemical Physics, Vol. 115, Issue 8
  • DOI: 10.1063/1.1388543

Triggering dynamics of the high-pressure benzene amorphization
journal, December 2006

  • Ciabini, Lucia; Santoro, Mario; Gorelli, Federico A.
  • Nature Materials, Vol. 6, Issue 1
  • DOI: 10.1038/nmat1803

Molecules under extreme conditions: Chemical reactions at high pressure
journal, January 2003

  • Schettino, Vincenzo; Bini, Roberto
  • Physical Chemistry Chemical Physics, Vol. 5, Issue 10
  • DOI: 10.1039/b301381b

Critical factors affecting chemical reactions on polymers
journal, January 1968

  • Gaylord, Norman G.
  • Journal of Polymer Science Part C: Polymer Symposia, Vol. 24, Issue 1
  • DOI: 10.1002/polc.5070240103

Interpretation of Raman spectra of disordered and amorphous carbon
journal, May 2000

Linearly Polymerized Benzene Arrays As Intermediates, Tracing Pathways to Carbon Nanothreads
journal, November 2015

  • Chen, Bo; Hoffmann, Roald; Ashcroft, N. W.
  • Journal of the American Chemical Society, Vol. 137, Issue 45
  • DOI: 10.1021/jacs.5b09053

Systematic Enumeration of sp 3 Nanothreads
journal, July 2015

Crystal Structure of Benzene II at 25 Kilobars
journal, September 1969

Pressure-frozen benzene I revisited
journal, January 2006

  • Budzianowski, Armand; Katrusiak, Andrzej
  • Acta Crystallographica Section B Structural Science, Vol. 62, Issue 1
  • DOI: 10.1107/S010876810503747X

Note: Simple and portable setup for loading high purity liquids in diamond anvil cell
journal, March 2016

  • Olejnik, Ella; Deemyad, Shanti
  • Review of Scientific Instruments, Vol. 87, Issue 3
  • DOI: 10.1063/1.4943258

Specific volume measurements of Cu, Mo, Pd, and Ag and calibration of the ruby R 1 fluorescence pressure gauge from 0.06 to 1 Mbar
journal, June 1978

  • Mao, H. K.; Bell, P. M.; Shaner, J. W.
  • Journal of Applied Physics, Vol. 49, Issue 6
  • DOI: 10.1063/1.325277

High-pressure x-ray diffraction studies on rhenium up to 216 GPa (2.16 Mbar)
journal, December 1987

  • Vohra, Yogesh K.; Duclos, Steven J.; Ruoff, Arthur L.
  • Physical Review B, Vol. 36, Issue 18
  • DOI: 10.1103/PhysRevB.36.9790

EXPGUI , a graphical user interface for GSAS
journal, April 2001

The structure and dynamics of solid benzene. I. A neutron powder diffraction study of deuterated benzene from 4 K to the melting point
journal, May 1993

  • Craven, C. J.; Hatton, P. D.; Howard, C. J.
  • The Journal of Chemical Physics, Vol. 98, Issue 10
  • DOI: 10.1063/1.464528

EosFit7c and a Fortran module (library) for equation of state calculations
journal, January 2014

  • Angel, Ross J.; Alvaro, Matteo; Gonzalez-Platas, Javier
  • Zeitschrift für Kristallographie - Crystalline Materials, Vol. 229, Issue 5
  • DOI: 10.1515/zkri-2013-1711

Ab initio molecular dynamics for open-shell transition metals
journal, November 1993

Efficiency of ab-initio total energy calculations for metals and semiconductors using a plane-wave basis set
journal, July 1996

Van der Waals density functionals applied to solids
journal, May 2011

First-principles calculations of the ferroelastic transition between rutile-type and CaCl 2 -type SiO 2 at high pressures
journal, October 2008

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