DOI: 10.1063/1.1379764. Comparison of four methods to compute the dielectric permittivity of liquids from molecular dynamics simulations

Comparison of four methods to compute the dielectric permittivity of liquids from molecular dynamics simulations

10.1063/1.1379764

Crossref journal-article

AIP Publishing

The Journal of Chemical Physics (317)

Abstract

Four methods to compute the dielectric permittivity ε of a liquid from molecular simulations are compared in the context of the simple point charge (SPC) water model. In the first method (unrestrained method), ε is evaluated from the fluctuations of the box dipole moment M, monitored during a single equilibrium simulation. In the three other methods, ε is evaluated from the probability distribution p(M) of the dipole moment norm. This distribution is itself evaluated in three different ways: (i) from multiple simulations involving a M-dependent biasing potential (umbrella-sampling method), (ii) from multiple simulations involving a constrained dipole moment norm (M-constraint method), or (iii) from fitting of incomplete p(M) estimates to a Maxwell distribution (fitting method). The four methods are shown to converge to an identical estimate of ε=61±1 for SPC water (256 molecules, reaction-field electrostatics). The convergence properties, advantages, and drawbacks of the different methods are analyzed in detail.

Bibliography

Heinz, T. N., van Gunsteren, W. F., & HÃ¼nenberger, P. H. (2001). Comparison of four methods to compute the dielectric permittivity of liquids from molecular dynamics simulations. The Journal of Chemical Physics, 115(3), 1125â1136.

Authors 3

Tim N. Heinz (first)
Wilfred F. van Gunsteren (additional)
Philippe H. Hünenberger (additional)

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Dates

Type	When
Created	23 years, 1 month ago (July 26, 2002, 9:26 a.m.)
Deposited	1 year, 6 months ago (Feb. 6, 2024, 1:24 a.m.)
Indexed	3 weeks, 5 days ago (Aug. 6, 2025, 8:28 a.m.)
Issued	24 years, 1 month ago (July 15, 2001)
Published	24 years, 1 month ago (July 15, 2001)
Published Print	24 years, 1 month ago (July 15, 2001)

Funders 0

None

BibTeX

@article{Heinz_2001, title={Comparison of four methods to compute the dielectric permittivity of liquids from molecular dynamics simulations}, volume={115}, ISSN={1089-7690}, url={http://dx.doi.org/10.1063/1.1379764}, DOI={10.1063/1.1379764}, number={3}, journal={The Journal of Chemical Physics}, publisher={AIP Publishing}, author={Heinz, Tim N. and van Gunsteren, Wilfred F. and Hünenberger, Philippe H.}, year={2001}, month=jul, pages={1125–1136} }

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  "abstract": "<jats:p>Four methods to compute the dielectric permittivity \u03b5 of a liquid from molecular simulations are compared in the context of the simple point charge (SPC) water model. In the first method (unrestrained method), \u03b5 is evaluated from the fluctuations of the box dipole moment M, monitored during a single equilibrium simulation. In the three other methods, \u03b5 is evaluated from the probability distribution p(M) of the dipole moment norm. This distribution is itself evaluated in three different ways: (i) from multiple simulations involving a M-dependent biasing potential (umbrella-sampling method), (ii) from multiple simulations involving a constrained dipole moment norm (M-constraint method), or (iii) from fitting of incomplete p(M) estimates to a Maxwell distribution (fitting method). The four methods are shown to converge to an identical estimate of \u03b5=61\u00b11 for SPC water (256 molecules, reaction-field electrostatics). The convergence properties, advantages, and drawbacks of the different methods are analyzed in detail.</jats:p>",
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