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Computational Investigation of the Solvation of Nitric Acid:Formation of the NOs and H_3O+Ion Pair

机译:硝酸溶剂化的计算研究:NO和H_3O +离子对的形成

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MP2 and B3LYP calculations were performed on complexes of nitric acid with water using the 6-311++G-(2d,p)basis set to determine optimized geometries and binding energies for HNO_3...nH_2O systems(n = 1-4).The structures for the global minima for n = 1-4 have homodromic rings formed by successive hydrogen bonds.The potential energy surface for the HNO_3...nH_2O clusters is quite shallow.The first stable ion-pair configuration is obtained for a HNO_3...4H_2O complex.The ion pair,H_3O~+-NO_3~-,is separated by the three H_2O molecules forming an Eigen-ion(H_9O_4~+)type structure.The transition states and activation barriers for n = 1-4 were also determined.The zero-point corrected transition-state barrier for the ion pair is only 0.5 kcal/mol.Larger HNO_3...nH_2O clusters(n up to 32)were also determined to be dominated by the ion-pair motif.
机译:使用6-311 ++ G-(2d,p),对硝酸与水的络合物进行MP2和B3LYP计算,以确定HNO_3 ... nH_2O系统(n = 1-4)的最佳几何构型和结合能n = 1-4的全局极小值的结构具有由连续的氢键形成的等规环.HNO_3 ... nH_2O团簇的势能表面很浅.HNO_3获得了第一个稳定的离子对构型... 4H_2O络合物。离子对H_3O〜+ -NO_3〜-被三个H_2O分子隔开,形成本征离子(H_9O_4〜+)型结构,n = 1-4时的跃迁态和激活势垒离子对的零点校正过渡态势垒仅为0.5 kcal / mol.HNO_3 ... nH_2O较大的簇(n最多为32)也被确定为离子对基序的主体。

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