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首页> 外文期刊>The journal of physical chemistry, B. Condensed matter, materials, surfaces, interfaces & biophysical >Theoretical Study of Temperature and Solvent Dependence of the Free-Energy Surface of the Intramolecular Electron-Transfer Based on the RISM-SCF Theory:Application to the 1,3-Dinitrobenzene Radical Anion in Acetonitrile and Methanol
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Theoretical Study of Temperature and Solvent Dependence of the Free-Energy Surface of the Intramolecular Electron-Transfer Based on the RISM-SCF Theory:Application to the 1,3-Dinitrobenzene Radical Anion in Acetonitrile and Methanol

机译：基于RISM-SCF理论的分子内电子转移自由能表面的温度和溶剂依赖性的理论研究：在乙腈和甲醇中的1,3-二硝基苯自由基阴离子中的应用

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摘要

The free-energy surfaces along the intramolecular electron-transfer reaction path of the 1,3-dinitrobenzene radical anion in acetonitrile and methanol are investigated with the reference interaction site model self-consistent field theory.Although acetonitrile and methanol have similar values of the dielectric constant,the free-energy profiles are quite different.In the methanol solution,the charge is strongly localized on one of the nitrile substituents due to a strong hydrogen bond between 1,3-dinitrobenzene and the solvent,while the polarization is not so large in the case of acetonitrile.The temperature dependence of the reorganization energy,the coupling strength,and the activation barrier is evaluated in both acetonitrile and methanol.The reorganization energy and the activation barrier decrease with increasing temperature for both cases.The electronic coupling strength also shows a similar tendency in the temperature dependence;it increases with increasing temperature in both solvents but with different rates.The behavior is explained in terms of the strong polarization induced by the hydrogen bond between the solute and solvent in the methanol solution.
机译：利用参考相互作用位点模型自洽场理论研究了1,3-二硝基苯自由基阴离子在乙腈和甲醇中沿分子内电子转移反应路径的自由能表面，尽管乙腈和甲醇的介电值相似在甲醇溶液中，由于1,3-二硝基苯和溶剂之间的强氢键，电荷强烈地位于一个腈取代基上，而极化作用并不大在乙腈和甲醇中，评估了重组能，偶联强度和活化势垒的温度依赖性。在两种情况下，重组能和活化垒均随着温度的升高而降低。在温度依赖性上显示出相似的趋势;在两种情况下都随温度升高而增加溶剂的行为不同，但速率不同。用甲醇溶液中溶质和溶剂之间的氢键引起的强极化来解释其行为。

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