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

Zhu, Tianyu and Van Voorhis, Troy (2021) Understanding the Dipole Moment of Liquid Water from a Self-Attractive Hartree Decomposition. Journal of Physical Chemistry Letters, 12 (1). pp. 6-12. ISSN 1948-7185.

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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.

Item Type:Article
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URLURL TypeDescription Paper - 12/03/2020
Zhu, Tianyu0000-0003-2061-3237
Van Voorhis, Troy0000-0001-7111-0176
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.
Funding AgencyGrant Number
Subject Keywords:dipole moment; DFT; liquid water; density partitioning
Issue or Number:1
Record Number:CaltechAUTHORS:20201104-131743072
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Official Citation:Understanding the Dipole Moment of Liquid Water from a Self-Attractive Hartree Decomposition. Tianyu Zhu and Troy Van Voorhis. The Journal of Physical Chemistry Letters 2021 12 (1), 6-12; DOI: 10.1021/acs.jpclett.0c03300
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:106430
Deposited By: Tony Diaz
Deposited On:05 Nov 2020 00:46
Last Modified:21 Jan 2021 18:03

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