Havriliak–Negami relaxation

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The Havriliak–Negami relaxation is an empirical modification of the Debye relaxation model in electromagnetism. Unlike the Debye model, the Havriliak–Negami relaxation accounts for the asymmetry and broadness of the dielectric dispersion curve. The model was first used to describe the dielectric relaxation of some polymers,[1] by adding two exponential parameters to the Debye equation:

where is the permittivity at the high frequency limit, where is the static, low frequency permittivity, and is the characteristic relaxation time of the medium. The exponents and describe the asymmetry and broadness of the corresponding spectra.

Depending on application, the Fourier transform of the stretched exponential function can be a viable alternative that has one parameter less.

For the Havriliak–Negami equation reduces to the Cole–Cole equation, for to the Cole–Davidson equation.

Mathematical properties

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Real and imaginary parts

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The storage part   and the loss part   of the permittivity (here:   with  ) can be calculated as

 

and

 

with

 

Loss peak

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The maximum of the loss part lies at

 

Superposition of Lorentzians

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The Havriliak–Negami relaxation can be expressed as a superposition of individual Debye relaxations

 

with the real valued distribution function

 

where

 

if the argument of the arctangent is positive, else[2]

 

Noteworthy,   becomes imaginary valued for

 

and complex valued for

 

Logarithmic moments

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The first logarithmic moment of this distribution, the average logarithmic relaxation time is

 

where   is the digamma function and   the Euler constant.[3]

Inverse Fourier transform

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The inverse Fourier transform of the Havriliak-Negami function (the corresponding time-domain relaxation function) can be numerically calculated.[4] It can be shown that the series expansions involved are special cases of the Fox–Wright function.[5] In particular, in the time-domain the corresponding of   can be represented as

 

where   is the Dirac delta function and

 

is a special instance of the Fox–Wright function and, precisely, it is the three parameters Mittag-Leffler function[6] also known as the Prabhakar function. The function   can be numerically evaluated, for instance, by means of a Matlab code .[7]

See also

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References

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  1. ^ Havriliak, S.; Negami, S. (1967). "A complex plane representation of dielectric and mechanical relaxation processes in some polymers". Polymer. 8: 161–210. doi:10.1016/0032-3861(67)90021-3.
  2. ^ Zorn, R. (1999). "Applicability of Distribution Functions for the Havriliak–Negami Spectral Function". Journal of Polymer Science Part B. 37 (10): 1043–1044. Bibcode:1999JPoSB..37.1043Z. doi:10.1002/(SICI)1099-0488(19990515)37:10<1043::AID-POLB9>3.3.CO;2-8.
  3. ^ Zorn, R. (2002). "Logarithmic moments of relaxation time distributions" (PDF). Journal of Chemical Physics. 116 (8): 3204–3209. Bibcode:2002JChPh.116.3204Z. doi:10.1063/1.1446035.
  4. ^ Schönhals, A. (1991). "Fast calculation of the time dependent dielectric permittivity for the Havriliak-Negami function". Acta Polymerica. 42: 149–151.
  5. ^ Hilfer, J. (2002). "H-function representations for stretched exponential relaxation and non-Debye susceptibilities in glassy systems". Physical Review E. 65: 061510. Bibcode:2002PhRvE..65f1510H. doi:10.1103/physreve.65.061510.
  6. ^ Gorenflo, Rudolf; Kilbas, Anatoly A.; Mainardi, Francesco; Rogosin, Sergei V. (2014). Springer (ed.). Mittag-Leffler Functions, Related Topics and Applications. ISBN 978-3-662-43929-6.
  7. ^ Garrappa, Roberto. "The Mittag-Leffler function". Retrieved 3 November 2014.