Fractional Viscosity Dependence of Reaction Kinetics in Glass-Forming Liquids

조회수 : 40 등록일 : 2017.09.19 00:00

저자 : Kwon, S (Kwon, Seulki); Sung, BJ (Sung, Bong June)
출판일 : 2017.08.25

Fractional Viscosity Dependence of Reaction Kinetics in Glass-Forming Liquids

Kwon, S (Kwon, Seulki)1,2 ] Cho, HW (Cho, Hyun Woo)1,2 ] Kim, J (Kim, Jeongmin)1,2 ] Sung, BJ (Sung, Bong June)1,2 ]

[ 1 ] Sogang Univ, Dept Chem, Seoul 121742, South Korea
[ 2 ] Sogang Univ, Res Inst Basic Sci, Seoul 121742, South Korea

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 eta(s), i.e., D similar to eta(-xi D)(s) with xi(D) = 0.85. The dynamic heterogeneity of a KA liquid affects the rate constant k(rxn) of the loop formation and leads to the identical fractional dependence of k(rxn) on eta(s) with k(rxn) similar to eta(-xi)(s) and xi = xi(D), contrary to reactions in dynamically homogeneous solutions where k(rxn) similar to eta(-1)(s).

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