Deuterium isotope effects in polymerization of benzene under pressure

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

doi:10.1021/acs.jpclett.7b00536

Title: Deuterium isotope effects in polymerization of benzene under pressure

Journal Article · Mon Apr 10 00:00:00 EDT 2017 · Journal of Physical Chemistry Letters

DOI:https://doi.org/10.1021/acs.jpclett.7b00536· OSTI ID:1366413

^[1]; Dunuwille, Mihindra ^[1];

^[2]; Taylor, Trevor V. ^[1]; Hinton, Jasmine K. ^[1]; MacLean, Mary C. ^[1]; Molaison, Jamie J. ^[3]; dos Santos, Antonio M. ^[3]; Sinogeikin, Stanislav ^[4];

^[1]

Univ. of Utah, Salt Lake City, UT (United States)
Northwestern Univ., Evanston, IL (United States)
Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
Carnegie Institute of Washington, Argonne, IL (United States)

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.

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Research Organization:: Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Spallation Neutron Source (SNS)

Sponsoring Organization:: USDOE

Grant/Contract Number:: AC05-00OR22725

OSTI ID:: 1366413

Journal Information:: Journal of Physical Chemistry Letters, Vol. 8, Issue 8; ISSN 1948-7185

Publisher:: American Chemical SocietyCopyright Statement

Country of Publication:: United States

Language:: English

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Cited by: 11 works

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