A surprisingly simple correlation between the classical and quantum structural networks in liquid water

作者：Hamm Peter^*; Fanourgakis George S; Xantheas Sotiris S^*

来源：Journal of Chemical Physics, 2017, 147(6): 064506.

DOI：10.1063/1.4993166

Nuclear quantum effects in liquid water have profound implications for several of its macroscopic properties related to the structure, dynamics, spectroscopy, and transport. Although several of water's macroscopic properties can be reproduced by classical descriptions of the nuclei using interaction potentials effectively parameterized for a narrow range of its phase diagram, a proper account of the nuclear quantum effects is required to ensure that the underlying molecular interactions are transferable across a wide temperature range covering different regions of that diagram. When performing an analysis of the hydrogen-bonded structural networks in liquid water resulting from the classical (class) and quantum (qm) descriptions of the nuclei with two interaction potentials that are at the two opposite ends of the range in describing quantum effects, namely the flexible, pair-wise additive q-TIP4P/F, and the flexible, polarizable TTM3-F, we found that the (class) and (qm) results can be superimposed over the temperature range T = 250-350 K using a surprisingly simple, linear scaling of the two temperatures according to T-(qm) = alpha T-(class) + Delta T, where alpha = 0.99 and Delta T = -6 K for q-TIP4P/F and alpha = 1.24 and Delta T = -64 K for TTM3-F. This simple relationship suggests that the structural networks resulting from the quantum and classical treatment of the nuclei with those two very different interaction potentials are essentially similar to each other over this extended temperature range once a model-dependent linear temperature scaling lawis applied. Published by AIP Publishing.

• 出版日期2017-8-14