Ab Initio Simulation of Liquid Water without Artificial High Temperature.

ABSTRACT

Comprehending the structure and dynamics of water is crucial in various fields, such as water desalination, ion separation, electrocatalysis, and biochemical processes. While reported works show that the ab initio molecular dynamics (AIMD) can accurately portray water's structure, the artificial high temperature (AHT) from 120 to 30 K is needed to mimic the quantum nature of hydrogen-bond network from GGA, metaGGA to hybrid functionals. The AHT proves to be an inadequate approach for systems involving aqueous multiphase mixtures, such as water-solid interfaces and aqueous solutions. This is due to the activation of additional phonons in other phases, which can lead to an overestimation of the dynamics of nearby water molecules. In this work, we find that the regularized SCAN (rSCAN) functional effectively captures both the structure and dynamics of liquid water at ambient conditions without AHT. Moreover, rSCAN closely matches experimental results for the hydration structures of alkali, alkali earth, and halide ions. We anticipate that the versatile and accurate rSCAN functional will emerge as a key tool based on ab initio simulation for investigating chemical processes in aqueous environments.