Heavy (or large) ions in a fluid in an electric field: The diffusion equation exactly following from the Fokker-Planck equation

J Chem Phys. 2008 Jul 28;129(4):044903. doi: 10.1063/1.2957461.

Abstract

The problem of the derivation of the diffusion equation exactly following from the Fokker-Planck (or Klein-Kramers) equation for heavy (or large) particles in a fluid in an external force field is solved in the case in which the particles are ions subject to a uniform (but in general time-varying) electric field. It is found that such a diffusion equation maintains memory of the initial ion velocity distribution, unless sufficiently large values of time are considered. In such temporal asymptotic limit, the diffusion equation exactly becomes (i) the Smoluchowski equation when the electric field is constant in time, and (ii) a new equation generalizing the Smoluchowski equation, when the electric field is arbitrarily time varying. Finally, it is shown that the obtained exact (or asymptotic) results make questionable the procedures and the results of approximate theories developed in the past to get a "corrected" Smoluchowski equation when the external force can also be, in general, position dependent.

MeSH terms

  • Diffusion
  • Electricity*
  • Electromagnetic Fields
  • Gases / chemistry
  • Ions / chemistry

Substances

  • Gases
  • Ions