Molecular polarizability of water from local dielectric response theory
Abstract
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:
-
- Brookhaven National Lab. (BNL), Upton, NY (United States). Center for Functional Nanomaterials (CFN)
- Publication Date:
- Research Org.:
- Brookhaven National Laboratory (BNL), Upton, NY (United States)
- Sponsoring Org.:
- USDOE Office of Science (SC), Basic Energy Sciences (BES)
- OSTI Identifier:
- 1376181
- Alternate Identifier(s):
- OSTI ID: 1374458
- 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
- Resource 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)
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 36 MATERIALS SCIENCE
Citation Formats
Ge, Xiaochuan, and Lu, Deyu. Molecular polarizability of water from local dielectric response theory. United States: N. p., 2017.
Web. doi:10.1103/PhysRevB.96.075114.
Ge, Xiaochuan, & Lu, Deyu. Molecular polarizability of water from local dielectric response theory. United States. https://doi.org/10.1103/PhysRevB.96.075114
Ge, Xiaochuan, and Lu, Deyu. Tue .
"Molecular polarizability of water from local dielectric response theory". United States. https://doi.org/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 = {Tue Aug 08 00:00:00 EDT 2017},
month = {Tue Aug 08 00:00:00 EDT 2017}
}
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