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Computing the Kirkwood g-Factor by Combining Constant Maxwell Electric Field and Electric Displacement Simulations: Application to the Dielectric Constant of Liquid Water.

Published version
Peer-reviewed

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Authors

Zhang, Chao 
Hutter, Jürg 

Abstract

In his classic 1939 paper, Kirkwood linked the macroscopic dielectric constant of polar liquids to the local orientational order as measured by the g-factor (later named after him) and suggested that the corresponding dielectric constant at short-range is effectively equal to the macroscopic value just after "a distance of molecular magnitude" [ Kirkwood, J. Chem. Phys., 1939, 7, 911 ]. Here, we show a simple approach to extract the short-ranged Kirkwood g-factor from molecular dynamics (MD) simulation by superposing the outcomes of constant electric field E and constant electric displacement D simulations [ Zhang and Sprik, Phys. Rev. B: Condens. Matter Mater. Phys., 2016, 93, 144201 ]. Rather than from the notoriously slow fluctuations of the dipole moment of the full MD cell, the dielectric constant can now be estimated from dipole fluctuations at short-range, accelerating the convergence. Exploiting this feature, we computed the bulk dielectric constant of liquid water modeled in the generalized gradient approximation (PBE) to density functional theory and found it to be at least 40% larger than the experimental value.

Description

Keywords

0307 Theoretical and Computational Chemistry

Journal Title

J Phys Chem Lett

Conference Name

Journal ISSN

1948-7185
1948-7185

Volume Title

7

Publisher

American Chemical Society (ACS)
Sponsorship
Engineering and Physical Sciences Research Council (EP/K014560/1)
The research fellowship (Grant ZH 477/1-1) awarded to C.Z. by the Deutsche Forschungsgemeinschaft (DFG) is gratefully acknowledged. Computational resources were provided by the UK Car−Parrinello (UKCP) consortium funded by the Engineering and Physical Sciences Research Council (EPSRC).
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