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Published January 14, 2021 | Supplemental Material + Submitted
Journal Article Open

Understanding the Dipole Moment of Liquid Water from a Self-Attractive Hartree Decomposition

Abstract

The dipole moment of a single water molecule in liquid water has been a critical concept for understanding water's dielectric properties. In this work, we investigate the dipole moment of liquid water through a self-attractive Hartree (SAH) decomposition of total electron density computed by density functional theory, on water clusters sampled from ab initio molecular dynamics simulation of bulk water. By adjusting one parameter that controls the degree of density localization, we reveal two distinct pictures of water dipoles that are consistent with bulk dielectric properties: a localized picture with smaller and less polarizable monomer dipoles and a delocalized picture with larger and more polarizable monomer dipoles. We further uncover that the collective dipole–dipole correlation is stronger in the localized picture and is key to connecting individual dipoles with bulk dielectric properties. On the basis of these findings, we suggest considering both individual and collective dipole behaviors when studying the dipole moment of liquid water and propose new design strategies for developing water models.

Additional Information

© 2020 American Chemical Society. Received: November 3, 2020; Accepted: December 7, 2020; Published: December 9, 2020. This work was funded by a grant from the NSF CHE-1900358. We thank Piotr de Silva for inspiring discussions. The authors declare no competing financial interest.

Attached Files

Submitted - Understanding_the_Dipole_Moment_of_Liquid_Water_from_a_Self-Attractive_Hartree_Decomposition_v2.pdf

Supplemental Material - jz0c03300_si_001.pdf

Files

Understanding_the_Dipole_Moment_of_Liquid_Water_from_a_Self-Attractive_Hartree_Decomposition_v2.pdf

Additional details

Created:
September 22, 2023
Modified:
October 23, 2023