Diffusion-Influenced Reversible Geminate ABCD Reaction in the Presence of an External Field

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• 作者：Soohyung Park ; Kook Joe Shin
• 刊名：Journal of Physical Chemistry B
• 出版年：2008
• 出版时间：May 15, 2008
• 年：2008
• 卷：112
• 期：19
• 页码：6241 - 6249
• 全文大小：137K
• 年卷期：v.112,no.19(May 15, 2008)
• ISSN：1520-5207

文摘

We investigate a diffusion-influenced ground-state reversible geminate ABCD reaction in the presence of aconstant external field in one dimension. In the Laplace domain, we first obtain the nonreactive Green functionfrom which the reactive Green function is derived. Analytic asymptotic expressions of the survival probabilityare obtained in the time domain for both short and long time regions. There exist four regimes for theequilibrium survival probability according to the signs of the field intensities a₁ and a₂ that reactant andproduct states feel, respectively. Analysis of the long-time asymptotic behavior of the survival probabilityshows two regimes depending on the sign of a parameter K(mages/entities/equiv.gif">ibe/journals/jpcbfk/112/i19/eqn/jp075933xe10001.gif">D₂ - ibe/journals/jpcbfk/112/i19/eqn/jp075933xe10002.gif">D₁), where D₁ and D₂ are the relativediffusion constants of corresponding states, respectively. Combining these two results, we predict a total ofeight regimes for the long-time asymptotic behavior of the survival probability. We find that the long-timeasymptotic behavior of the deviation of the effective survival probability shows the t^-3/2 power law whenm(mages/entities/equiv.gif"> min {ibe/journals/jpcbfk/112/i19/eqn/jp075933xe10003.gif">D₁, ibe/journals/jpcbfk/112/i19/eqn/jp075933xe10004.gif">D₂}) mages/entities/ne.gif"> 0, whereas it shows t^-1/2 power law when m = 0. When one of the fields is turnedoff, the long-time asymptotic behavior of the survival probability shows a kinetic transition as the sign of theremaining field changes.