Electronic Structure Insights into the Solvation of Magnesium Ions with Cyclic and Acyclic Carbonates.
Electronic Structure Insights into the Solvation of Magnesium Ions with Cyclic and Acyclic Carbonates.
复制标题
镁离子与环状和无环碳酸盐溶剂化的电子结构见解。
作者：
Mehdi Shakourian;G. Kamath;S. Sankaranarayanan
利用分子动力学模拟和密度泛函理论对碳酸盐中Mg（2+）的溶剂化行为进行了研究。在M06-2X/6-311++G（d，p）水平上计算了碳酸酯与Mg（2+）的结合能和溶剂化自由能，并结合ABF-MD模拟计算了碳酸酯与Mg（2+）的溶剂化自由能，发现碳酸亚乙酯（EC）和碳酸亚乙酯：碳酸亚丙酯（EC：PC）二元混合物是与Mg（2+）相互作用的最佳碳酸酯溶剂.分子中原子的自然键轨道和量子理论分析支持热化学计算，在Mg（2+）（EC）和Mg（2+）（EC：PC）络合物中观察到电荷转移、微扰稳定能、电子密度和Wiberg键指数的最高值。非共价相互作用的图表明，那些负责形成镁（2+）碳酸盐络合物是强到弱的吸引力的相互作用，这取决于相互作用的区域。最后，态密度计算表明，Mg（2+）和碳酸酯溶剂之间的相互作用会影响所有碳酸酯溶剂的HOMO和LUMO态，并将它们移动到更负的能量值。
A computational framework to rank the solvation behavior of Mg(2+) in carbonates by using molecular dynamics simulations and density functional theory is reported. Based on the binding energies and enthalpies of solvation calculated at the M06-2X/6-311++G(d,p) level of theory and the free energies of solvation from ABF-MD simulations, we find that ethylene carbonate (EC) and the ethylene carbonate:propylene carbonate (EC:PC) binary mixture are the best carbonate solvents for interacting with Mg(2+) . Natural bond orbital and quantum theory of atoms in molecules analyses support the thermochemistry calculations with the highest values of charge transfer, perturbative stabilization energies, electron densities, and Wiberg bond indices being observed in the Mg(2+) (EC) and Mg(2+) (EC:PC) complexes. The plots of the noncovalent interactions indicate that those responsible for the formation of Mg(2+) carbonate complexes are strong-to-weak attractive interactions, depending on the regions that are interacting. Finally, density of state calculations indicate that the interactions between Mg(2+) and the carbonate solvents affects the HOMO and LUMO states of all carbonate solvents and moves them to more negative energy values.
影响因子：
15
作者：
Johnson ER;Keinan S;Mori-Sánchez P;Contreras-García J;Cohen AJ;Yang W
通讯作者：
Yang W