Ferrari Leonardo
Dipartimento di Fisica, Universita' di Parma, Viale G.P. Usberti 7/A, I-43100 Parma, Italy.
J Chem Phys. 2008 Jul 28;129(4):044903. doi: 10.1063/1.2957461.
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.
对于处于外力场中的流体中的重(或大)粒子,从福克 - 普朗克(或克莱因 - 克拉默斯)方程精确推导扩散方程的问题,在粒子为受到均匀(但一般随时间变化)电场作用的离子的情况下得到了解决。结果发现,这样的扩散方程会保留初始离子速度分布的记忆,除非考虑足够大的时间值。在这种时间渐近极限下,当电场随时间恒定时,扩散方程精确地变为(i)斯莫卢霍夫斯基方程;当电场任意随时间变化时,扩散方程变为(ii)一个推广了斯莫卢霍夫斯基方程的新方程。最后,结果表明,当外力一般也可能与位置有关时,过去为得到“修正”的斯莫卢霍夫斯基方程而发展的近似理论的程序和结果因所获得的精确(或渐近)结果而受到质疑。