Department of Chemistry, Boston University, Boston, Massachusetts 02215, USA.
J Am Chem Soc. 2011 Jun 22;133(24):9441-50. doi: 10.1021/ja201695d. Epub 2011 May 27.
POLIR, a polarizable water potential optimized for vibrational and intermolecular spectroscopy in pure water but not optimized for solvation, is used to describe solutions of the divalent metal cations Ca(2+), Mg(2+), and Cu(2+). The spectral shifts in the O-H stretch region obtained from classical simulations are in agreement with experiment. The water-ion binding energies are dominated by classical electrostatics, even though the Cu(2+) case might be considered to involve an intermediate-strength chemical bond. Three-body energies of the ion with the first solvation shell are in agreement with ab initio calculations. Our results indicate the importance of polarization in the development of accurate, transferable, force fields and the power of classical methods when it is carefully included.
POLIR 是一种可极化水势能模型，专门针对纯水中的振动和分子间光谱学进行了优化，但并未针对溶剂化进行优化，可用于描述二价金属阳离子 Ca(2+)、Mg(2+)和 Cu(2+)的溶液。经典模拟得到的 O-H 伸缩区域的光谱位移与实验结果一致。水-离子结合能主要由经典静电作用决定，尽管 Cu(2+)的情况可能被认为涉及到中等强度的化学键。与第一个溶剂化壳层的离子的三体能量与从头计算一致。我们的结果表明，在开发准确、可转移的力场时，极化的重要性，以及当仔细包含时经典方法的强大功能。
