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Title: Communication: Dielectric properties of condensed systems composed of fragments

Abstract

Here, the dielectric properties of molecules and nanostructures are usually modified in a complex manner, when assembled into a condensed phase. We propose a first-principles method to compute polarizabilities of sub-entities of solids and liquids, which accounts for multipolar interactions at all orders and is applicable to semiconductors and insulators. The method only requires the evaluation of induced fields in the condensed phase, with no need of multiple calculations for each constituent. As an example, we present results for the molecular polarizabilities of water in a wide pressure and temperature range. We found that at ambient conditions, the dipole-induced-dipole approximation is sufficiently accurate and the Clausius-Mossotti relation may be used, e.g., to obtain molecular polarizabilities from experimental refractive indexes. However with increasing pressure, this approximation becomes unreliable and in the case of ice X the Clausius-Mossotti relation is not valid.

Authors:
ORCiD logo [1];  [2]; ORCiD logo [2]
  1. Hong Kong Univ. of Science and Technology, Hong Kong (China); HKUST Fok Ying Tung Research Institute, Guangzhou (China)
  2. Argonne National Lab. (ANL), Argonne, IL (United States); The Univ. of Chicago, Chicago, IL (United States)
Publication Date:
Research Org.:
Argonne National Lab. (ANL), Argonne, IL (United States)
Sponsoring Org.:
National Natural Science Foundation of China (NNSFC); Alfred P. Sloan Foundation; USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22). Materials Sciences & Engineering Division; Midwest Integrated Center for Computational Materials (MICCoM); USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22). Scientific User Facilities Division
OSTI Identifier:
1489283
Alternate Identifier(s):
OSTI ID: 1462597
Grant/Contract Number:  
AC02-06CH11357; MICCoM
Resource Type:
Accepted Manuscript
Journal Name:
Journal of Chemical Physics
Additional Journal Information:
Journal Volume: 149; Journal Issue: 5; Journal ID: ISSN 0021-9606
Publisher:
American Institute of Physics (AIP)
Country of Publication:
United States
Language:
English
Subject:
36 MATERIALS SCIENCE

Citation Formats

Pan, Ding, Govoni, Marco, and Galli, Giulia. Communication: Dielectric properties of condensed systems composed of fragments. United States: N. p., 2018. Web. doi:10.1063/1.5044636.
Pan, Ding, Govoni, Marco, & Galli, Giulia. Communication: Dielectric properties of condensed systems composed of fragments. United States. doi:10.1063/1.5044636.
Pan, Ding, Govoni, Marco, and Galli, Giulia. Thu . "Communication: Dielectric properties of condensed systems composed of fragments". United States. doi:10.1063/1.5044636. https://www.osti.gov/servlets/purl/1489283.
@article{osti_1489283,
title = {Communication: Dielectric properties of condensed systems composed of fragments},
author = {Pan, Ding and Govoni, Marco and Galli, Giulia},
abstractNote = {Here, the dielectric properties of molecules and nanostructures are usually modified in a complex manner, when assembled into a condensed phase. We propose a first-principles method to compute polarizabilities of sub-entities of solids and liquids, which accounts for multipolar interactions at all orders and is applicable to semiconductors and insulators. The method only requires the evaluation of induced fields in the condensed phase, with no need of multiple calculations for each constituent. As an example, we present results for the molecular polarizabilities of water in a wide pressure and temperature range. We found that at ambient conditions, the dipole-induced-dipole approximation is sufficiently accurate and the Clausius-Mossotti relation may be used, e.g., to obtain molecular polarizabilities from experimental refractive indexes. However with increasing pressure, this approximation becomes unreliable and in the case of ice X the Clausius-Mossotti relation is not valid.},
doi = {10.1063/1.5044636},
journal = {Journal of Chemical Physics},
number = 5,
volume = 149,
place = {United States},
year = {2018},
month = {8}
}

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