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Title: Non-linear and non-local behaviour in spontaneously electrical solids

Abstract

Using reflection–absorption infrared spectroscopy (RAIRS), we show that solids displaying spontaneous dipole orientation possess quite general non-local and non-linear characteristics, exemplified through their internal electric fields. The most graphic illustration of this, uncovered originally through electron beam studies, may be found in films of cis-methyl formate (cis-MF), for which data demonstrated the counter-intuitive property that the degree of dipole order in the film does not monotonically decrease as the temperature of deposition rises, but rather increases sharply above ~77 K. Here we show how RAIRS provides independent evidence to support this conclusion. These new data confirm (i) that the behaviour of spontelectrics is governed by an expression for the degree of dipole orientation, which is continuous in temperature, but with a discontinuity in the derivative, and (ii) that the temperature of deposition associated with this discontinuity matches the temperature above which dipole order switches from the expected reduction with temperature to an increase with temperature.

Authors:
ORCiD logo [1];  [1]; ORCiD logo [1]; ORCiD logo [1];  [1]; ORCiD logo [1]; ORCiD logo [1]; ORCiD logo [2]; ORCiD logo [2]
  1. Institute of Chemical Sciences; Heriot-Watt University; Edinburgh; UK
  2. Department of Physics and Astronomy; University of Aarhus; Aarhus; Denmark
Publication Date:
Research Org.:
Lawrence Berkeley National Laboratory-National Energy Research Scientific Computing Center
Sponsoring Org.:
USDOE Office of Science (SC)
OSTI Identifier:
1492846
DOE Contract Number:  
AC02-05CH11231
Resource Type:
Journal Article
Journal Name:
Physical Chemistry Chemical Physics. PCCP (Print)
Additional Journal Information:
Journal Volume: 20; Journal Issue: 7; Journal ID: ISSN 1463-9076
Publisher:
Royal Society of Chemistry
Country of Publication:
United States
Language:
English

Citation Formats

Roman, M., Taj, S., Gutowski, M., McCoustra, M. R. S., Dunn, A. C., Keolopile, Z. G., Rosu-Finsen, A., Cassidy, A. M., and Field, D. Non-linear and non-local behaviour in spontaneously electrical solids. United States: N. p., 2018. Web. doi:10.1039/c7cp08489g.
Roman, M., Taj, S., Gutowski, M., McCoustra, M. R. S., Dunn, A. C., Keolopile, Z. G., Rosu-Finsen, A., Cassidy, A. M., & Field, D. Non-linear and non-local behaviour in spontaneously electrical solids. United States. doi:10.1039/c7cp08489g.
Roman, M., Taj, S., Gutowski, M., McCoustra, M. R. S., Dunn, A. C., Keolopile, Z. G., Rosu-Finsen, A., Cassidy, A. M., and Field, D. Mon . "Non-linear and non-local behaviour in spontaneously electrical solids". United States. doi:10.1039/c7cp08489g.
@article{osti_1492846,
title = {Non-linear and non-local behaviour in spontaneously electrical solids},
author = {Roman, M. and Taj, S. and Gutowski, M. and McCoustra, M. R. S. and Dunn, A. C. and Keolopile, Z. G. and Rosu-Finsen, A. and Cassidy, A. M. and Field, D.},
abstractNote = {Using reflection–absorption infrared spectroscopy (RAIRS), we show that solids displaying spontaneous dipole orientation possess quite general non-local and non-linear characteristics, exemplified through their internal electric fields. The most graphic illustration of this, uncovered originally through electron beam studies, may be found in films of cis-methyl formate (cis-MF), for which data demonstrated the counter-intuitive property that the degree of dipole order in the film does not monotonically decrease as the temperature of deposition rises, but rather increases sharply above ~77 K. Here we show how RAIRS provides independent evidence to support this conclusion. These new data confirm (i) that the behaviour of spontelectrics is governed by an expression for the degree of dipole orientation, which is continuous in temperature, but with a discontinuity in the derivative, and (ii) that the temperature of deposition associated with this discontinuity matches the temperature above which dipole order switches from the expected reduction with temperature to an increase with temperature.},
doi = {10.1039/c7cp08489g},
journal = {Physical Chemistry Chemical Physics. PCCP (Print)},
issn = {1463-9076},
number = 7,
volume = 20,
place = {United States},
year = {2018},
month = {1}
}

Works referenced in this record:

Dipole-Oriented Molecular Solids Can Undergo a Phase Change and Still Maintain Electrical Polarization
journal, October 2016

  • Cassidy, Andrew; Jørgensen, Mads R. V.; Rosu-Finsen, Alexander
  • The Journal of Physical Chemistry C, Vol. 120, Issue 42
  • DOI: 10.1021/acs.jpcc.6b07296

Spontaneously electrical solids in a new light
journal, January 2015

  • Lasne, Jérôme; Rosu-Finsen, Alexander; Cassidy, Andrew
  • Physical Chemistry Chemical Physics, Vol. 17, Issue 32
  • DOI: 10.1039/C5CP03174E

Long-range interactions between polar molecules and metallic surfaces: A comparison of classical and density functional theory based models
journal, March 2009


Electron affinities of the first‐row atoms revisited. Systematic basis sets and wave functions
journal, May 1992

  • Kendall, Rick A.; Dunning, Thom H.; Harrison, Robert J.
  • The Journal of Chemical Physics, Vol. 96, Issue 9
  • DOI: 10.1063/1.462569

Transverse optical to longitudinal optical splitting and dipole moment derivatives from infrared spectra of thin films of molecular solids
journal, April 1991

  • Jones, Llewellyn H.; Swanson, Basil I.
  • The Journal of Physical Chemistry, Vol. 95, Issue 7
  • DOI: 10.1021/j100160a016

Spontaneous Dipole Alignment in Films of N 2 O
journal, February 2009


A review of recent progress in understanding the spontelectric state of matter
journal, June 2017

  • Plekan, Oksana; Rosu-Finsen, Alexander; Cassidy, Andrew M.
  • The European Physical Journal D, Vol. 71, Issue 6
  • DOI: 10.1140/epjd/e2017-80048-3

Corrected electrostatic model for dipoles adsorbed on a metal surface
journal, November 1994

  • Maschhoff, Brian L.; Cowin, James P.
  • The Journal of Chemical Physics, Vol. 101, Issue 9
  • DOI: 10.1063/1.468241

Adsorption and Thermal Processing of Glycolaldehyde, Methyl Formate, and Acetic Acid on Graphite at 20 K
journal, June 2015

  • Burke, Daren J.; Puletti, Fabrizio; Woods, Paul M.
  • The Journal of Physical Chemistry A, Vol. 119, Issue 26
  • DOI: 10.1021/acs.jpca.5b04010

Wannier-Mott Excitons in Nanoscale Molecular Ices
journal, October 2017


Intermolecular Interactions between Molecules in Various Conformational States: The Dimer of Oxalic Acid
journal, June 2014

  • Keolopile, Zibo G.; Ryder, Matthew R.; Gutowski, Maciej
  • The Journal of Physical Chemistry A, Vol. 118, Issue 35
  • DOI: 10.1021/jp4125638

Coupled-cluster theory in quantum chemistry
journal, February 2007


Formation of methyl formate after cosmic ion irradiation of icy grain mantles
journal, September 2010


Spontaneous polarization of solid CO on water ices and some astrophysical implications
journal, January 2016

  • Rosu-Finsen, Alexander; Lasne, Jérôme; Cassidy, Andrew
  • Physical Chemistry Chemical Physics, Vol. 18, Issue 7
  • DOI: 10.1039/C5CP07049J

Spontaneous electric fields in films of cis-methyl formate
journal, January 2012

  • Plekan, Oksana; Cassidy, Andrew; Balog, Richard
  • Physical Chemistry Chemical Physics, Vol. 14, Issue 28
  • DOI: 10.1039/c2cp41229b

Gaussian basis sets for use in correlated molecular calculations. I. The atoms boron through neon and hydrogen
journal, January 1989

  • Dunning, Thom H.
  • The Journal of Chemical Physics, Vol. 90, Issue 2
  • DOI: 10.1063/1.456153