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Quasi-chemical theory of F−(aq): The “no split occupancies rule” revisited
The Journal of Chemical Physics ( IF 4.4 ) Pub Date : 2017-09-12 , DOI: 10.1063/1.4986244
Mangesh I. Chaudhari 1 , Susan B. Rempe 1 , Lawrence R. Pratt 2
Affiliation  

We use ab initio molecular dynamics (AIMD) calculations and quasi-chemical theory (QCT) to study the inner-shell structure of F(aq) and to evaluate that single-ion free energy under standard conditions. Following the “no split occupancies” rule, QCT calculations yield a free energy value of −101 kcal/mol under these conditions, in encouraging agreement with tabulated values (−111 kcal/mol). The AIMD calculations served only to guide the definition of an effective inner-shell constraint. QCT naturally includes quantum mechanical effects that can be concerning in more primitive calculations, including electronic polarizability and induction, electron density transfer, electron correlation, molecular/atomic cooperative interactions generally, molecular flexibility, and zero-point motion. No direct assessment of the contribution of dispersion contributions to the internal energies has been attempted here, however. We anticipate that other aqueous halide ions might be treated successfully with QCT, provided that the structure of the underlying statistical mechanical theory is absorbed, i.e., that the “no split occupancies” rule is recognized.

中文翻译:

的F准化学理论- (水):“无裂占用规则”再访

我们使用从头算分子动力学(AIMD)计算和准化学理论(QCT)研究F的内壳层结构-(aq)并评估标准条件下的单离子自由能。遵循“无分割占用”规则,在这些条件下,QCT计算得出的自由能值为-101 kcal / mol,这鼓励与列表值一致(-111 kcal / mol)。AIMD计算仅用于指导有效内壳约束的定义。QCT自然地包括在更原始的计算中可能涉及的量子力学效应,包括电子极化率和感应,电子密度转移,电子相关性,通常的分子/原子协作相互作用,分子柔性和零点运动。但是,这里没有尝试直接评估色散对内部能量的贡献。
更新日期:2017-11-01
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