分子动力学模拟揭示了离子配对在水和非水电解质溶液（如甲醇）中对离子溶剂化壳层结构和动力学的影响。研究发现，离子配对概率取决于离子-溶剂相互作用和离子间库仑力的平衡。锂氟（LiF）由于其强烈的库仑吸引显示出最高的离子配对概率。在甲醇中，由于其较低的介电常数，离子配对概率高于水。随着离子或反离子尺寸增大，配对概率下降。溶剂分子的协调数和平均驻留时间受离子间吸引力影响，而势能面和溶剂分子的平均驻留时间分析揭示了离子溶剂化壳层稳定性的变化如何受到离子间吸引力和其他溶剂性质的影响。
摘要：
Molecular dynamics simulations were performed to understand the ionic association and its effect on the structure and dynamics of ion solvation shell in aqueous and non-aqueous electrolyte solutions (water and methanol). The simulation results show that the probability of ion pairing depends on the interplay between ion-solvent interactions on the one hand, and Coulomb forces between ion and its counter-ion on the other hand. The highest probability of ion-pairing is observed for LiF due to the strong Columbic attraction between Li+ and F- ions. This is evident from the calculated radial distribution functions and orientation of solvent molecules which show signatures of ionic association in water and methanol. Due to low dielectric constant of methanol, the probability of ionic association is higher in methanol than water and the probability of ionic association decreases with increasing size of ion or counter- ion. The coordination number and mean residence time is found to be influenced by the inter- ionic attraction. Detailed analysis of Potential of Mean Force (PMFs) and Mean Residence Time (MRT) of solvent molecules reveal how the stability of ionic solvation shell is influenced by the inter-ionic attraction and other properties of the solvent.
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