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Title: Lone Pair Rotational Dynamics in Solids

Abstract

Traditional classifications of crystalline phases focus on nuclear degrees of freedom. Through examination of both electronic and nuclear structure, we introduce the concept of an electronic plastic crystal. Such a material is classified by crystalline nuclear structure, while localized electronic degrees of freedom — here lone pairs — exhibit orientational motion at finite temperatures. This orientational motion is an emergent phenomenon arising from the coupling between electronic structure and polarization fluctuations generated by collective motions, such as phonons. Using ab initio molecular dynamics simulations, we predict the existence of electronic plastic crystal motion in halogen crystals and halide perovskites, and suggest that such motion may be found in a broad range of solids with lone pair electrons. Finally, such fluctuations in the charge density should be observable, in principle via synchrotron scattering.

Authors:
ORCiD logo [1];  [2]
  1. Rutgers Univ., Piscataway, NJ (United States)
  2. Temple Univ., Philadelphia, PA (United States)
Publication Date:
Research Org.:
Energy Frontier Research Centers (EFRC) (United States). Center for Complex Materials from First Principles (CCM); Temple Univ., Philadelphia, PA (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES); US Army Research Office (ARO); National Science Foundation (NSF)
OSTI Identifier:
1601234
Alternate Identifier(s):
OSTI ID: 1599673
Grant/Contract Number:  
SC0012575; 1625061; W911FN-16-2-0189
Resource Type:
Accepted Manuscript
Journal Name:
Physical Review Letters
Additional Journal Information:
Journal Volume: 124; Journal Issue: 6; Journal ID: ISSN 0031-9007
Publisher:
American Physical Society (APS)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; chemical bonding; crystal phenomena; electric polarization; electronic structure; first-principles calculations; wannier function methods

Citation Formats

Remsing, Richard C., and Klein, Michael L. Lone Pair Rotational Dynamics in Solids. United States: N. p., 2020. Web. doi:10.1103/PhysRevLett.124.066001.
Remsing, Richard C., & Klein, Michael L. Lone Pair Rotational Dynamics in Solids. United States. doi:https://doi.org/10.1103/PhysRevLett.124.066001
Remsing, Richard C., and Klein, Michael L. Fri . "Lone Pair Rotational Dynamics in Solids". United States. doi:https://doi.org/10.1103/PhysRevLett.124.066001. https://www.osti.gov/servlets/purl/1601234.
@article{osti_1601234,
title = {Lone Pair Rotational Dynamics in Solids},
author = {Remsing, Richard C. and Klein, Michael L.},
abstractNote = {Traditional classifications of crystalline phases focus on nuclear degrees of freedom. Through examination of both electronic and nuclear structure, we introduce the concept of an electronic plastic crystal. Such a material is classified by crystalline nuclear structure, while localized electronic degrees of freedom — here lone pairs — exhibit orientational motion at finite temperatures. This orientational motion is an emergent phenomenon arising from the coupling between electronic structure and polarization fluctuations generated by collective motions, such as phonons. Using ab initio molecular dynamics simulations, we predict the existence of electronic plastic crystal motion in halogen crystals and halide perovskites, and suggest that such motion may be found in a broad range of solids with lone pair electrons. Finally, such fluctuations in the charge density should be observable, in principle via synchrotron scattering.},
doi = {10.1103/PhysRevLett.124.066001},
journal = {Physical Review Letters},
number = 6,
volume = 124,
place = {United States},
year = {2020},
month = {2}
}

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