Fractional Viscosity Dependence of Reaction Kinetics in Glass-Forming Liquids

Seulki Kwon, Hyun Woo Cho, Jeongmin Kim, and Bong June Sung
Phys. Rev. Lett. 119, 087801 – Published 25 August 2017
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Abstract

The diffusion of molecules in complex systems such as glasses and cell cytoplasm is slow, heterogeneous, and sometimes nonergodic. The effects of such intriguing diffusion on the kinetics of chemical and biological reactions remain elusive. In this Letter, we report that the kinetics of the polymer loop formation reaction in a Kob-Andersen (KA) glass forming liquid is influenced significantly by the dynamic heterogeneity. The diffusion coefficient D of a KA liquid deviates from the Stokes-Einstein relation at low temperatures and D shows a fractional dependence on the solvent viscosity ηs, i.e., DηsξD with ξD=0.85. The dynamic heterogeneity of a KA liquid affects the rate constant krxn of the loop formation and leads to the identical fractional dependence of krxn on ηs with krxnηsξ and ξ=ξD, contrary to reactions in dynamically homogeneous solutions where krxnηs1.

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  • Received 13 January 2017

DOI:https://doi.org/10.1103/PhysRevLett.119.087801

© 2017 American Physical Society

Physics Subject Headings (PhySH)

Interdisciplinary PhysicsPolymers & Soft MatterPhysics of Living SystemsStatistical Physics & ThermodynamicsCondensed Matter, Materials & Applied Physics

Authors & Affiliations

Seulki Kwon, Hyun Woo Cho, Jeongmin Kim, and Bong June Sung*

  • Department of Chemistry and Research Institute for Basic Science, Sogang University, Seoul 121-742, Republic of Korea

  • *bjsung@sogang.ac.kr

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Issue

Vol. 119, Iss. 8 — 25 August 2017

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