Riera Marc, Götz Andreas W, Paesani Francesco
Department of Chemistry and Biochemistry, University of California, San Diego, La Jolla, California 92093, USA.
San Diego Supercomputer Center, University of California, San Diego, La Jolla, California 92093, USA.
Phys Chem Chem Phys. 2016 Nov 9;18(44):30334-30343. doi: 10.1039/c6cp02553f.
A new set of i-TTM potential energy functions describing the interactions between alkali metal ions and water molecules is reported. Following our previous study on halide ion-water interactions [J. Phys. Chem. B, 2016, 120, 1822], the new i-TTM potentials are derived from fits to CCSD(T) reference energies and, by construction, are compatible with the MB-pol many-body potential, which has been shown to accurately predict the properties of water from the gas to the condensed phase. Within the i-TTM formalism, two-body repulsion, electrostatic, and dispersion energies are treated explicitly, while many-body effects are represented by classical induction. The accuracy of the new i-TTM potentials is assessed through extensive comparisons with results obtained from different ab initio methods, including CCSD(T), CCSD(T)-F12b, DF-MP2, and several DFT models, as well as from polarizable force fields for M(HO) clusters with M = Li, Na, K, Rb, and Cs, and n = 1-4.
报道了一组新的描述碱金属离子与水分子相互作用的i-TTM势能函数。继我们之前关于卤离子-水相互作用的研究[《物理化学杂志B》，2016年，120卷，1822页]之后，新的i-TTM势能是通过对CCSD(T)参考能量进行拟合得到的，并且通过构建，与MB-pol多体势能兼容，MB-pol多体势能已被证明能够准确预测从气相到凝聚相的水的性质。在i-TTM形式体系中，明确处理了两体排斥能、静电能和色散能，而多体效应则由经典诱导来表示。通过与从不同的从头算方法（包括CCSD(T)、CCSD(T)-F12b、DF-MP2和几种DFT模型）以及与M = Li、Na、K、Rb和Cs且n = 1 - 4的M(HO)簇的可极化力场获得的结果进行广泛比较，评估了新的i-TTM势能的准确性。
