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Title: Molecular polarizability of water from local dielectric response theory

Here, we propose a fully ab initio theory to compute the electron density response under the perturbation in the local field. This method is based on our recently developed local dielectric response theory [Phys. Rev. B 92, 241107(R), 2015], which provides a rigorous theoretical framework to treat local electronic excitations in both nite and extended systems beyond the commonly employed dipole approximation. We have applied this method to study the electronic part of the molecular polarizability of water in ice Ih and liquid water. Our results reveal that the crystal field of the hydrogen-bond network has strong anisotropic effects, which significantly enhance the out-of-plane component and suppress the in-plane component perpendicular to the bisector direction. The contribution from the charge transfer is equally important, which increases the isotropic molecular polarizability by 5-6%. Our study provides new insights into the dielectric properties of water, which form the basis to understand electronic excitations in water and to develop accurate polarizable force fields of water.
Authors:
 [1] ;  [1]
  1. Brookhaven National Lab. (BNL), Upton, NY (United States). Center for Functional Nanomaterials (CFN)
Publication Date:
Report Number(s):
BNL-114164-2017-JA
Journal ID: ISSN 2469-9950; PRBMDO; R&D Project: 16068; KC0403020; TRN: US1702801
Grant/Contract Number:
SC0012704; AC02-05CH11231
Type:
Accepted Manuscript
Journal Name:
Physical Review B
Additional Journal Information:
Journal Volume: 96; Journal Issue: 7; Journal ID: ISSN 2469-9950
Publisher:
American Physical Society (APS)
Research Org:
Brookhaven National Laboratory (BNL), Upton, NY (United States)
Sponsoring Org:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
Country of Publication:
United States
Language:
English
Subject:
36 MATERIALS SCIENCE
OSTI Identifier:
1376181
Alternate Identifier(s):
OSTI ID: 1374458

Ge, Xiaochuan, and Lu, Deyu. Molecular polarizability of water from local dielectric response theory. United States: N. p., Web. doi:10.1103/PhysRevB.96.075114.
Ge, Xiaochuan, & Lu, Deyu. Molecular polarizability of water from local dielectric response theory. United States. doi:10.1103/PhysRevB.96.075114.
Ge, Xiaochuan, and Lu, Deyu. 2017. "Molecular polarizability of water from local dielectric response theory". United States. doi:10.1103/PhysRevB.96.075114. https://www.osti.gov/servlets/purl/1376181.
@article{osti_1376181,
title = {Molecular polarizability of water from local dielectric response theory},
author = {Ge, Xiaochuan and Lu, Deyu},
abstractNote = {Here, we propose a fully ab initio theory to compute the electron density response under the perturbation in the local field. This method is based on our recently developed local dielectric response theory [Phys. Rev. B 92, 241107(R), 2015], which provides a rigorous theoretical framework to treat local electronic excitations in both nite and extended systems beyond the commonly employed dipole approximation. We have applied this method to study the electronic part of the molecular polarizability of water in ice Ih and liquid water. Our results reveal that the crystal field of the hydrogen-bond network has strong anisotropic effects, which significantly enhance the out-of-plane component and suppress the in-plane component perpendicular to the bisector direction. The contribution from the charge transfer is equally important, which increases the isotropic molecular polarizability by 5-6%. Our study provides new insights into the dielectric properties of water, which form the basis to understand electronic excitations in water and to develop accurate polarizable force fields of water.},
doi = {10.1103/PhysRevB.96.075114},
journal = {Physical Review B},
number = 7,
volume = 96,
place = {United States},
year = {2017},
month = {8}
}

Works referenced in this record:

Generalized Gradient Approximation Made Simple
journal, October 1996
  • Perdew, John P.; Burke, Kieron; Ernzerhof, Matthias
  • Physical Review Letters, Vol. 77, Issue 18, p. 3865-3868
  • DOI: 10.1103/PhysRevLett.77.3865