Leung Kevin, Rempe Susan B
Sandia National Laboratories, MS 1415 and 0316, Albuquerque, New Mexico 87185, USA.
J Am Chem Soc. 2004 Jan 14;126(1):344-51. doi: 10.1021/ja036267q.
We perform ab initio molecular dynamics simulations of the aqueous formate ion. The mean number of water molecules in the first solvation shell, or the hydration number, of each formate oxygen is found to be consistent with recent experiments. Our ab initio pair correlation functions, however, differ significantly from many classical force field results and hybrid quantum mechanics/molecular mechanics predictions. They yield roughly one less hydrogen bond between each formate oxygen and water than force field or hybrid methods predict. Both the BLYP and PW91 exchange correlation functionals give qualitatively similar results. The time dependence of the hydration numbers are examined, and Wannier function techniques are used to analyze electronic configurations along the molecular dynamics trajectory.
我们对甲酸根离子水溶液进行了从头算分子动力学模拟。发现每个甲酸根氧原子的第一溶剂化层中的平均水分子数，即水合数，与最近的实验结果一致。然而，我们的从头算对关联函数与许多经典力场结果以及量子力学/分子力学混合预测有显著差异。与力场或混合方法的预测相比，它们得出的每个甲酸根氧原子与水之间的氢键大约少一个。BLYP和PW91交换关联泛函都给出了定性相似的结果。研究了水合数的时间依赖性，并使用Wannier函数技术沿着分子动力学轨迹分析电子构型。
