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The static structure of a bulk electrolyte solution or colloid system is investigated in the framework of a dressed-ion theory (DIT). The number–number, charge–number, and charge–charge...
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Frequency and wave-vector dependent dielectric function of water: Collective modes and relaxation spectra

J. Chem. Phys. 109, 1939 (1998); doi:10.1063/1.476884

Issue Date: 1 August 1998

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Philippe A. Bopp
Laboratoire de Physico-Chimie Moléculaire, Université Bordeaux I, 351 Cours de Libération, F-33405 Talence Cedex, France

Alexei A. Kornyshev and Godehard Sutmann
Institut für Energieverfahrenstechnik, Forschungszentrum Jülich, GmbH, D-52425 Jülich, Germany
The longitudinal frequency and wave-vector dependent complex dielectric response function chi(k,omega) = 1 – 1/epsilon(k,omega) is calculated in a broad range of k values by means of molecular dynamics computer simulation for a central force model of water. Its imaginary part, i.e., Im{epsilon(k,omega)}/| epsilon(k,omega)|2, shows two main contributions in the region of small k values: Debye-like orientational relaxation in the lower frequency part of the spectrum and a damped librational resonance at the high frequency wing. The Debye relaxation time does not follow a de Gennes-like pattern: tau(k) goes through a maximum at k [approximate] k* [approximate] 1.7 Å–1, while the static polar structure factor S(k) peaks at k [approximate] 3 Å–1. The resonance frequency omega(k) and the decay decrement gamma(k) show a dispersion law, indicative of a decaying optical-like mode, the libron. With an approximate normal mode approach, we analyze the origin of this mode on a molecular level which shows that it is due to a damped propagation of molecular orientational vibrations through the network of hydrogen bonds. At high k the decay, due to dissipation of collective into single particle motions, dominates. The static dielectric function is calculated on the basis of the response function spectra via the Kramers–Kronig relation. In the small k region epsilon(k) decreases from the macroscopic value epsilon [approximate] 80 to a value [approximate] 15, i.e. it exhibits a Lorentzian-type behavior. This behavior is shown to be determined by higher order multipole correlation functions. In the intermediate and high k range, our results on epsilon(k) and chi(k) are in excellent agreement with data extracted from experimental partial pair correlation functions: epsilon(k) exhibits two divergence points on the k axis with a range of negative values in between where a maximum in chi(k) is found with chimax(k) >> 1, indicative of overscreening. Consequences of quantum corrections to chi(k) with respect to a purely classical calculation are discussed and consequences are shown for the interaction energy between hydrated ions. ©1998 American Institute of Physics.
History: Received 28 April 1997; accepted 3 February 1998
Permalink: http://link.aip.org/link/?JCPSA6/109/1939/1
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KEYWORDS and PACS

Keywords
PACS
  • 71.45.Gm
    Electronic structure Collective effects Exchange, correlation, dielectric and magnetic functions, plasmons
  • 61.20.Ja
    Structure of solids and liquids; crystallography Structure of liquids Computer simulation of liquid structure
  • 61.43.Bn
    Structure of solids and liquids; crystallography Disordered solids Structural modeling: serial-addition models, computer simulation
  • YEAR: 1998

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REFERENCES (95)
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