Accessing the Accuracy of Density Functional Theory through Structure and Dynamics of the Water-Air Interface.

ABSTRACT: Density functional theory-based molecular dynamics simulations are increasingly being used for simulating aqueous interfaces. Nonetheless, the choice of the appropriate density functional, critically affecting the outcome of the simulation, has remained arbitrary. Here, we assess the performance of various exchange-correlation (XC) functionals, based on the metrics relevant to sum-frequency generation spectroscopy. The structure and dynamics of water at the water-air interface are governed by heterogeneous intermolecular interactions, thereby providing a critical benchmark for XC functionals. We find that the XC functionals constrained by exact functional conditions (revPBE and revPBE0) with the dispersion correction show excellent performance. The poor performance of the empirically optim

SUBMITTER: Ohto T 

PROVIDER: S-EPMC6748669 | biostudies-literature | 2019 Sep

REPOSITORIES: biostudies-literature