Structure and Dynamics of Water at the Water-Air Interface Using First-Principles Molecular Dynamics Simulations. II. NonLocal vs Empirical van der Waals Corrections.

Abstract

van der Waals (vdW) correction schemes have been recognized to be essential for an accurate description of liquid water in first-principles molecular dynamics simulation. The description of the structure and dynamics of water is governed by the type of the vdW corrections. So far, two vdW correction schemes have been often used: empirical vdW corrections and nonlocal vdW corrections. In this paper, we assess the influence of the empirical vs nonlocal vdW correction schemes on the structure and dynamics of water at the water–air interface. Since the structure of water at the water–air interface is established by a delicate balance of hydrogen bond formation and breaking, the simulation at the water–air interface provides a unique platform to testify as to the heterogeneous interaction of water. We used the metrics [Ohto et al. J. Chem. Theory Comput., 2019, 15, 595−60230468702] which are directly connected with the sum-frequency generation spectroscopic measurement. We find that the overall performance of nonlocal vdW methods is either similar or worse compared to the empirical vdW methods. We also investigated the performance of the optB88-DRSLL functional, which showed slightly less accuracy than the revPBE-D3 method. We conclude that the revPBE-D3 method shows the best performance for describing the interfacial water.