Using our polarizable force-field models and employing classical rate theories of chemical reactions, we examine the ethylene carbonate (EC) exchange process between the first and second solvation shells around Li⁺ and the dissociation kinetics of ion pairs Li⁺–[BF₄] and Li⁺–[PF₆] in this solvent. We calculate the exchange rates using transition state theory and correct them with transmission coefficients computed by the reactive flux, Impey, Madden, and McDonald approaches, and Grote-Hynes theory. We found that the residence times of EC around Li⁺ ions varied from 60 to 450 ps, depending on the correction method used. We found that the relaxation times changed significantly from Li⁺–[BF₄] to Li⁺–[PF₆] ion pairs in EC. Our results also show that, in addition to affecting the free energy of dissociation in EC, the anion type also significantly influences the dissociation kinetics of ion pairing.

中文翻译：

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李⁺溶剂化和Li的动力学⁺ -BF ₄ ^- / PF ₆ ^-中的碳酸亚乙酯离子对。基于经典速率理论的分子动力学研究

使用我们可极化的力场模型，并使用经典的化学反应速率理论，我们研究了围绕Li ⁺的第一和第二溶剂化壳之间的碳酸亚乙酯（EC）交换过程以及离子对Li ⁺ -[BF ₄ ]的离解动力学。在该溶剂中为Li ⁺ -[PF ₆ ]。我们使用过渡状态理论计算汇率，并使用由无功通量，Impey，Madden和McDonald方法以及Grote-Hynes理论计算出的传输系数来校正汇率。我们发现，根据所使用的校正方法，EC在Li ⁺离子周围的停留时间从60 ps至450 ps不等。我们发现弛豫时间与Li相比有显着变化EC中的⁺ – [BF ₄ ]到Li ⁺ – [PF ₆ ]离子对。我们的结果还表明，除了影响EC中解离的自由能外，阴离子类型还显着影响离子对的解离动力学。