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Simulating dielectric spectra: A demonstration of the direct electric field method and a new model for the nonlinear dielectric response

Journal Article · · Journal of Chemical Physics
DOI:https://doi.org/10.1063/5.0143425· OSTI ID:2422110
 [1];  [2];  [3];  [3];  [2];  [4];  [2]
  1. Theiss Research, La Jolla, CA (United States); National Inst. of Standards and Technology (NIST), Gaithersburg, MD (United States). Material Measurement Laboratory; OSTI
  2. National Inst. of Standards and Technology (NIST), Gaithersburg, MD (United States). Material Measurement Laboratory
  3. National Inst. of Standards and Technology (NIST), Boulder, CO (United States). Communications Technology Laboratory
  4. Rensselaer Polytechnic Inst., Troy, NY (United States)
+ Show Author Affiliations
Here we demonstrate a method to compute the dielectric spectra of fluids in molecular dynamics (MD) by directly applying electric fields to the simulation. We obtain spectra from MD simulations with low magnitude electric fields (≈0.01 V/Å) in agreement with spectra from the fluctuation–dissipation method for water and acetonitrile. We examine this method’s trade-off between noise at low field magnitudes and the nonlinearity of the response at higher field magnitudes. We then apply the Booth equation to describe the nonlinear response of both fluids at low frequency (0.1 GHz) and high field magnitude (up to 0.5 V/Å). We develop a model of the frequency-dependent nonlinear response by combining the Booth description of the static nonlinear dielectric response of fluids with the frequency-dependent linear dielectric response of the Debye model. We find good agreement between our model and the MD simulations of the nonlinear dielectric response for both acetonitrile and water.
Research Organization:
Rensselaer Polytechnic Inst., Troy, NY (United States)
Sponsoring Organization:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
Grant/Contract Number:
SC0022247
OSTI ID:
2422110
Alternate ID(s):
OSTI ID: 1964202
Journal Information:
Journal of Chemical Physics, Journal Name: Journal of Chemical Physics Journal Issue: 12 Vol. 158; ISSN 0021-9606
Publisher:
American Institute of Physics (AIP)Copyright Statement
Country of Publication:
United States
Language:
English

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Figures / Tables (8)

FIG. 1(p. 3)figure FIG. 1
FIG. 2(p. 4)figure FIG. 2
FIG. 3(p. 4)figure FIG. 3
TABLE I(p. 4)table TABLE I
FIG. 4(p. 5)figure FIG. 4
FIG. 5(p. 6)figure FIG. 5
FIG. 6(p. 7)figure FIG. 6
FIG. 7(p. 8)figure FIG. 7

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Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
Chemical compounds
Chemistry
Debye model
Dielectric properties
Dielectric spectroscopy
Electric fields
Electrostatics
Linear response
Molecular dynamics
Nonequilibrium statistical mechanics
Physics
Statistical thermodynamics