Isotope Effects in Liquid Water via Deep Potential Molecular Dynamics [article]

Hsin-Yu Ko, Linfeng Zhang, Biswajit Santra, Han Wang, Weinan E, Robert A. DiStasio Jr., Roberto Car
2019 arXiv   pre-print
A comprehensive microscopic understanding of ambient liquid water is a major challenge for ab initio simulations as it simultaneously requires an accurate quantum mechanical description of the underlying potential energy surface (PES) as well as extensive sampling of configuration space. Due to the presence of light atoms (e.g., H or D), nuclear quantum fluctuations lead to observable changes in the structural properties of liquid water (e.g., isotope effects), and therefore provide yet another
more » ... challenge for ab initio approaches. In this work, we demonstrate that the combination of dispersion-inclusive hybrid density functional theory (DFT), the Feynman discretized path-integral (PI) approach, and machine learning (ML) constitutes a versatile ab initio based framework that enables extensive sampling of both thermal and nuclear quantum fluctuations on a quite accurate underlying PES. In particular, we employ the recently developed deep potential molecular dynamics (DPMD) model---a neural-network representation of the ab initio PES---in conjunction with a PI approach based on the generalized Langevin equation (PIGLET) to investigate how isotope effects influence the structural properties of ambient liquid H_2O and D_2O. Through a detailed analysis of the interference differential cross sections as well as several radial and angular distribution functions, we demonstrate that this approach can furnish a semi-quantitative prediction of these subtle isotope effects.
arXiv:1904.04930v1 fatcat:isbacyfnnrbjrpcrbnwpu7t3s4